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By Robert M. Doerr

The oxidation kinetics of Ni-Y alloys in the range 0.04 to 8 weight-percent Y, and of high-purity Ni, were compared by the use of a sensitive volumetric apparatus. The reactions followed approximately the parabolic rate law; for oxidations in 02 at 0.5 atm and 1,200° C, the parabolic rate constant was about 0.37 + (0.064) (Y-2.11) mg cm-2 min-1/2, where Y represents the weight-percent Y in the alloy. Internal oxidation of Y occurred in the alloy specimens and the resultant Y203 particles, which were in patterns related to the eutectic structure of the alloys, served as markers showing that the subsequent oxidation of the surrounding Ni was by inward diffusion of O. The scale consisted in each case of NiO, but the inner parts of the scale on the alloy specimens included the patterned Y203 particles. The thicknesses of the inner parts of the scale depended directly on the Y concentration, and the thicknesses of the Y2O3-free outer parts of the scale were inversely related to the Y content of the alloys. There is thus a relationship between the thickness of the outer part of the scale and the protectivity of the scale. Outward diffusion of Ni and inward movement of 0, from the inner boundary of the Y2O3-free part of the scale, is proposed as a mechanism for these results.

Jan 1, 1966

By James Paone

The Bureau of Mines made drillability studies with impregnated diamond bits in the laboratory on 7 rock types and in the field on 21 different rock types. Results indicate that drill parameters of rotational speed, thrust, and torque must produce sufficient applied forces to induce stress levels that cause continuous failure in rock to achieve efficient penetration rates. Higher rotational speeds appear to be more effective in drilling relatively harder rocks, although the increased speed causes more bit wear; increases in thrust result in higher drilling rates but not linearly; and up to a critical value a linear relation exists between torque and penetration rate for a specific rock type. Penetration rates with impregnated bits show a trend similar to that obtained with surface-set bits for rock under 25,000 psi compressive strength.

Jan 1, 1966

By Frank B. Fulkerson

A study was made of scrap iron and steel in the South Central States in order to determine trends in processing, shipment, and consumption of this important commodity. These data were derived in part from statistical sources and in part by visits to scrap yards and steel mills. Trends in the industry were reviewed. Dealers in 1963 supplied 1.8 million tons of iron and steel scrap to steel mills and foundries in the south-central area, compared with 2.1 million tons in 1955. Most of the scrap was processed and shipped within 200 to 300 miles of consuming centers. Exports provide a principal outlet for dealers along the gulf coast. Most of the scrap that fills these orders is loaded onto freight cars at yards in Texas and Louisiana and -is shipped to ports for direct transfer from railroad car to ship. The tonnage exported varies greatly from year to year. The largest scrap operations are in or near large cities which are heavy scrap generating areas, steel mill sites, or port cities for export of scrap. A tentative analysis indicates that the short-run supply of prepared scrap is inelastic to price changes; therefore, buyers probably arc in a strong bargaining position at times of declining demand. One technological development in the iron and steel scrap industry is the use of large presses which can take complete automobiles with frames, wheels, springs, and other heavy parts still intact and reduce them to bundles. At Houston, Tex., and Kansas City, Mo., shredding plants are in operation that reduce car bodies and other light scrap into flat pieces 4 to 6 inches in size.

Jan 1, 1966

By R. L. Benner

A compound stability diagram was constructed by the Bureau of Mines for the Zn-Fe-S-O system to show the phases that should be thermodynamically stable at various temperatures, oxygen pressures, and SO2 pressures. The diagram was demonstrated to have good qualitative value for predicting stable phases that may, in turn, be related to the recovery of zinc in the leaching phase of the electrolytic zinc process. The study showed that roasting temperature is the most Significant variable in preventing roaster formation of zinc ferrite, which is directly related to subsequent extraction of zinc in the leaching step.

Jan 1, 1966

By Lester G. Morrell

THE WORLDWIDE economic expansion that has characterized the first 3 years of the 1960's continued through 1964 and was reflected in North America by strength in the industrial economy of the United States, which again was dominant. Advances in production were recorded in virtually all industries, including the mineral industry; 1964 mineral production established a new high, 5.4 percent above the previous peak recorded in 1963. However, the percentage increase in value of North American mineral production was slightly below overall economic growth. For industry in general, consumer demand held firm throughout the year and overall commodity prices averaged 2 percent higher than in 1963. Wages and salary payments also were up. With the single exception of the dock strike in the United States, the year was free of serious labor troubles and unemployment in both Canada and the States was at a low level. Despite the Viet-Nam situation, relatively tranquil international relations contributed to the forward movement of North American business. Total gross national product (GNP) for Canada and United States, in current dollars, was estimated at US$672.2 billion; 6.8 percent above the previous year's figure. Combined national income in 1964 amounted to US$546.9 billion, which was nearly 7.0 percent more than in 1963. In 1964, gains were recorded in each of more than 50 metals, nonmetals, and fuels commodities that comprise the North American output. The greatest category increase was 13 percent in metals, which was in part attributable to the 14 percent rise to a new record in value of iron and steel in United States, a 29 percent higher value of Canadian iron ore and a 57 percent rise in Canadian zinc. Despite a moderate decline in prices of iron ore and iron and steel products, generally favorable markets and rising prices for metallic ores and metals were a stimulant to the metals industry. Nonmetallic materials, with a total value in excess of US$5.25 billion were 7.3 percent higher than in 1963. High levels of highway and building construction and expanding demand for fertilizers and chemicals continued throughout the year. Noteworthy output increases were recorded for lime,

Jan 1, 1966

By Alla D. Mah

Compilation of data on materials of metallurgical interest is one of the important activities of the Berkeley Thermodynamics Laboratory of the Bureau of Mines. Recent renewed interest in metallurgy of vanadium renders the present compilation a timely guide for experimentation to improve present methods or to develop better methods of extractive metallurgy. Thermodynamic data for vanadium and its inorganic compounds have been critically surveyed, selected, and compiled into one convenient reference from which information can be readily obtained for evaluating heat balances, determining trends, and establishing limits of metallurgical processes. By indicating the direction of experimentation, this report enables the saving of time, effort, and expense which would otherwise be necessary for trial and error experimentation. Much of the data has been obtained experimentally at the Berkeley laboratory. Other data were collected through an extensive survey of worldwide literature through April 1965. Estimates were made when no data were avail-able. Data on the vanadium halides was sparse, and the results derived from existing data were at times divergent. Some of the selected values for the halides may need modification as more or better experimental data become available.

Jan 1, 1966

By E. Allen

Quebec Cartier Mining Company operates approximately two hundred and fifty pieces of equipment in a climate with a temperature that has averaged 27.5°F during the last seven years. The use of special-purpose lubricants, fuels, antifreeze, rubber compounds, and alloy steels have reduced the cold-weather hazards. In some areas, high-cost cold-weather protective heating devices are being eliminated with experience.

Jan 1, 1966

By G. C. Bernard, L. W. Bernard, L. W. Holm, W. L. Jacobs

The effect of loam on the permeability of porous media to water was studied as a {unction of foaming agent concentration, specific permeability, pressure gradient, length of a porous medium and its oil saturation. At a given fluid saturation in a porous medium, the permeability to water was found to be the same whether loam was present or not. Foam decreases the permeability to water by developing a higher trapped gas saturation than that obtained by water flooding without loam present, increasing the concentration of foaming agent increased the trapped gas saturation and thereby decreased the permeability to water. The presence of oil reduced the capability of most foaming agents to decrease the permeability of a porous medium to water. A few surfactants were found to be effective loaming agents even in the presence of oil. These results are similar to those reported in a previous paper on the effect of loam on the permeability of porous media to gas. The effect of loam was found to persist in long porous media at moderately high reservoir temperatures and during the passage of many pore volumes of surfactant-free water. INTRODUCTION This paper describes part of a study on a novel approach in the use of surfactants for oil recovery; the use of foam rather than water to displace oil. Previously it was found that foam can displace oil which normally is not displaced by water.4 The foam is formed by successively injecting a suitable surfactant solution and gas into a porous medium. Foam appears to have at least two uses in the field: (1) it shows promise as a superior oil recovery agent, and (2) it shows promise as a selective permeability reducing agent. Foam may be very useful in water floods, or in other oil recovery processes, where highly permeable streaks or unfavorable mobility ratios are a problem. A previous paper reported the effect of foam on the permeability of porous media to gas.1 In the present study the effect of foam on the permeability of porous media to water is reported. The specific objectives of the study were to determine: (1) the effect of foam on the permeability to water in porous media of various specific permeabilities, (2) the effect of foam on the permeability to water in the presence of oil, (3) the effect of foam and crude oil on the trapped gas saturation, (4) the effect of foam on permeability to water at trapped gas saturation, (5) the effect of pressure gradient on the permeability to water under foaming conditions, (6) the persistence of foam during the passage of surfactant-free water through the porous medium, and (7) the effect of various foaming agents, length of the porous medium and temperature on the permeability reduction caused by foam. EXPERIMENTAL PROCEDURES EQUIPMENT AND MATERIALS The experimental apparatus consisted of consolidated and unco n soli dated porous media, wet test meters and constant delivery pumps. The porous media consisted of consolidated sandstone cores (6 to 36 in. long), and unconsolidated sand packs (3 to 30 ft long). The consolidated cores had permeabilities of 32 and 1,000 md and porosities of about 20 per cent. The sand packs had permeabilities of 3,500 to 211,000 md and porosities of about 40 per cent. (Throughout this report a term such as 100 md sand" is used. This term means that the porous medium had a dry, nitrogen permeability of 100 md.) Fluids used in the experiments were distilled water, 1 per cent NaCl solution, aqueous solutions of foaming agents, nitrogen gas, air and crude oil.

Jan 1, 1966

By Alton B. Cook

A material balance equation was derived for calculating (1) the initial oil volume and (2) the relationship of average reservoir pressure to net gas in storage in reservoirs used for natural gas storage operations. The equation is also applicable to secondary-recovery operations where reservoirs are completely repressured and gas cycled. Using this equation minimized two probable sources of appreciable error in conventional material balance calculations: inaccurate measuring of and accounting for produced gas, and differences between true reservoir pressure and average reservoir pressures as derived from bottom-hole pressure measurements. A new procedure is presented for calculating water encroachment. By solving the conventional material balance equation and the derived equation for gas storage simultaneously, the values for initial oil in place and net water encroachment can both be determined.

Jan 1, 1966

By A. J. Conelius, D. P. Sobocinski

This paper presents a correlation for predicting the behavior of a water cone as it builds from the static water-oil contact to breakthrough conditions. The correlation is partly empirical and involves dimensionless groups of reservoir and fluid properties and of production and well characteristics. The groups were deduced from the scaling criteria for the immiscible displacement of oil by water. The correlation is based on a limited amount of experimenfal data from a laboratory sand-packed model and on results from a computer program for a two-dimensional, incompressible system. Because the correlating groups are dimensionless, they can be used to estimate the performance of water coning cases not specifically considered in the correlation. However, despite its dimensionless nature, the correlation is not completely general and will not provide meaningful estimates of cone behavior in many situations. INTRODUCTION AND BACKGROUND The production of water from oil wells is a common occurrence which increases the cost of producing operations and may reduce the efficiency of the depletion mechanism and the recovery of reserves. We will deal with one cause of this water production, namely, coning. The coning of water into a producing well is caused by pressure gradients established around the wellbore by the production of fluids from the well. These pressure gradients can raise the water-oil contact near the well where gradients are most severe. Gravity forces that arise from fluid density differences counterbalance the flowing pressure gradients and tend to keep the water out of the oil zone. Therefore, at any given time, there is a balance between gravitational and viscous forces at points on and away from the completion interval. When the dynamic forces at the wellbore exceed gravitational forces, a cone of water will ultimately break into the well to produce water along with the oil. We can expand on this basic visualization of coning by introducing the concepts of stable cone, unstable cone and critical production rate. For instance, if a well is produced at a constant rate and the pressure gradients in the drainage system have become constant, a steady-state condition is reached. If, at this condition, the dynamic forces at the well are less than the gravity forces, then the water or gas cone that has formed will not extend to the well. Moreover, the cone will neither advance nor recede, thus establishing what is known as a stable cone. Conversely, if the pressure in the system is in an unsteady-state condition, then an unstable cone will continue to advance until steady-state conditions prevail. If the flowing pressure drop at the well is suffcient to overcome the gravity forces, the unstable cone will grow and ultimately break into the well. It is important to note that in a realistic sense, stable cones may only be "pseudostable" because the drainage system and pressure distribution generally change. For example, with reservoir depletion, the water-oil contact may advance toward the completion interval, thereby increasing chances for coning. As another example, reduced productivity due to well damage requires a corresponding increase in the flowing pressure drop LO maintain a given production rate. This increase in pressure drop may force an otherwise stable cone into a well. The critical production rate, well known in the literature, is the rate above which the flowing pressure gradient at the well causes water (or gas) to cone into the well. It is, therefore, the maximum rate of oil production without concurrent production of the displacing phase by coning. At the critical rate, a built-up cone is stable but is at a position of incipient breakthrough. Numerous papers have been published on critical rates. Some of the better known of these include the work of (1) Muskat and Wyckoff,' who first dealt with the coning problem; (2) Chaney, et al,' who developed expressions similar to those of Muskat but who presented results in a conven ient-to-use graphical form (the "Sun" method); and (3) Meyer and Garder,b hose analysis is based on radial-flow formulas. One assumption in critical production rate analyses is that the cone has built-up to just before its breakthrough into the well. But, these analyses reveal nothing directly about the time it takes for the cone to build up to this incipient breakthrough position. Thus, water-free oil can be produced from a well for prolonged periods at rates above the critical rate before the well reaches the condition to which the critical rate applies. The published literature contains little on the rate of growth of a cone. Experimentally, Meyer and Searcy studied the rate of rise of a cone in a Hele-Shaw model.' Additional related work on water breakthrough and produced water-oil ratios in water driven reservoirs was reported by Muskat," Hutchinson and Kemp," Henley, et al,' and Stevens, et a1.B Theoretically, the basic coning equations for a water-oil system can be developed by applying the conservation of mass to each of the phases, relating flow velocities with pressure by Darcy's law, and relating pressures across water-oil interfaces by capillary pressure. With the usual boundaries at the well and reservoir limits, the solution of the resulting equations for the time behavior of a water-oil interface constitutes a free-surface, boundary-value problem. The shape of the boundary depends on the internal potential distribution, while this

Jan 1, 1966

By P. B. Demarsh

"Location: - On highway 59, 17 miles east of Val d 10r near junction of Montreal highway in Northwestern Quebec.Life; - Started production 1952, ceased 1965.Ore: - Pyrite, chalcopyrite and small amounts of free gold and goldsilver tellurides in narrow quartz-carbonate-tourmaline veins in granodiorite. Specific gravity 2, 70.Capacity: - 700 tons daily Bevcon ore supply, l 000 tons daily when custom ore available.Assay: - Heads 0 .140 oz. per ton; tails 0. 009 per ton; extraction 92.5%.Grind: - 75% minus 200 mesh at 700 tons; 68% minus 200 mesh at 1000 tons. Detention time 28 hours and 21 hours respectively.Treatment: - Cyanidation process.Reagents: - Per ton. Aero Cyanide (NaCn) 0, 50; crushed unslaked lime 1. 75; zinc 0. 03; litharge 0. 10; steel consumption 2. 25.Water: - Pumped from land-lock spring fed lake l 1/2 miles distant.Cost: - Per ton. Crushing 0. 13; grinding 0 .32; filtration 0. 07; cyanidation 0.14; miscellaneous 0.29; total 0.95.Power: - Hydro-electric, 25 cycle, 12, 000 volts reduced to 550 volts.Labour: - Predominantly French Canadian, nucleus English Canadians.Tailings: - Impounded low lying pond.Personnel: - 15 including supervision.Flow sheet: - Canadian Mining Manual l 9 5 6 .Building: - Wood truss construction: 3/ 4 in. siding, ten test and 1/ 4 in. transite outside. Corrugated galvanized iron roof. Ground level foundations. Internal self induced heating. Wood stave tank equipment."

Jan 1, 1966

By Webster S. Anderson

Bureau of Mines planer mining tests on the phosphate bed of the Douglas mine, near Drummond, Mont., indicated that a competent bed with a Mohs' scale hardness of 3 to 4 cannot be mined economically with the planer. Although planer mining was feasible where the bed was fractured enough for a 4-inch depth of cut to be consistently maintained, the depth of cut in the competent beds at the Douglas mine did not exceed 0.5 inch. Average production rates were 0.15 ton per minute and 9 tons per man-shift.

Jan 1, 1966

By M. M. Fine

This Bureau of Mines report describes the theory, experimental procedures, and the results obtained to date in the development of the Bureau's process for magnetically roasting iron ores using scrap iron as a means of reduction. Since magnetic separation is an operational step common to magnetic taconite plants, the preliminary research studies emphasized only the novel magnetic roasting step. The studies included the use of automobile scrap, ferrous reductants such as borings and turnings, and prereduced pellets. Technical feasibility of the process was demonstrated both on a bench- and pilot-scale. Quality magnetic concentrates with recoveries of over 90 percent were obtained from a direct shipping ore containing 59.5 percent Fe and from fine grained semitaconites with about 30 percent Fe.

Jan 1, 1966

By F. W. Jessen, C. C. Patton

Adsorbed films were formed on polished stainless steel specimens from dilute benzene solutions of two crude oil distillation residua. Although the two residua were extremely dissimilar in composition, contact angle measurements showed that the two films increased the wettability of the steel specimens to oil by equal amounts. Furthermore, the wettability of the films was essentially unaffected by the desorption techniques used. Paraffin deposits were formed from heptane-wax solutions on the same stainless steel specimens. These deposits definitely adhered to the surface. Presence of an adsorbed crude oil film on the metal surface increased its free surface energy and resulted in increased deposition of paraffin. The addition to the heptane - wax solution of small amounts of the same distillation residua that were used to form the adsorbed films resulted in decreased cohesive strength in the deposits formed, which resulted in decreased deposition. The presence of a crude oil fraction both in the solution and as a preadsorbed film eliminated the adherence of a deposit of any kind. A mechanism of deposition is proposed which explains the results obtained. INTRODUCTION The natural formation of any predominantly organic accumulation in oilwell tubing, surface flow lines or other production and storage facilities is called a paraffin deposit. These deposits restrict the production of crude oil, causing a substantial increase in production costs because of decreased flow capacity, expense for periodic deposit removal and unproductive downtime. The conditions under which such deposits form, their physical characteristics and the nature and severity of the problem created are extremely varied. Over the past several years, much progress has been made in developing and utilizing methods to remove accumulated paraffin deposition. However, like so many other problems, the basic stumbling block appears to be a lack of understanding of the fundamental mechanism involved in the formation of such deposits. Crude petroleum is known to contain considerable quantities of polar, surface active substances which Doddl has shown to be present at the oil-water interface. Denekas, Mattax and Davis2 observed that the wettability of reservoir rocks was drastically altered by exposure to crude oil fractions; and Zisman, et a1.3 showed that the nature of the compounds adsorbed on a surface would determine its wettability characteristics. Cole and Jessen4 and Ehrig5showed that surface wettability can have a profound effect on the magnitude of paraffin deposition, and Parks6 demonstrated chat the presence of certain adsorbed films on a metal surface would reduce the adherence of paraffin to that surface. Zisman7 has since advanced the theory that the conditions for adhesion are the same as for wetting. Therefore, it was felt that there was adequate evidence to support the supposition that adsorption of compounds from a crude oil might play an important part in paraffin deposition. ADSORPTION-WETTABILITY EXPERIMENTS Initial experiments were conducted to determine the effects of adsorption from solution of crude oil residua on the wettability of a polished stainless steel surface. Distillation residua with initial atmospheric boiling points of 700F were used in preference to the whole crudes in order to concentrate on the molecular weight range of interest, and to eliminate the possibility of composition change due to evaporation of the light ends. Also, these high boiling materials would be expected to be adsorbed from the whole oil in preference to similar compounds of lower molecular weight.

Jan 1, 1966

By Paul M. Buttermore

As part of a national canvass of water use the Bureau of Mines compiled data on water requirements in the petroleum and natural gas industries for the calendar year 1962, specifically in well drilling, secondary-recovery operations, and natural gas processing plants. Total new water use in the petroleum industry of the United States, excluding refining, was 5.3 billion barrels. Secondary-recovery operations and natural gas processing plants required about 2.5 billion barrels of new water input; each of these requirements was about eight times greater than that for well drilling. Total use, including recirculated water, was 45.3 billion barrels of which 3.4 billion barrels was consumed. The greatest use of recirculated water was for natural gas processing, amounting to 38.2 billion barrels. Projections of total water use show that by 1975, 75.4 billion barrels will be used by the petroleum industry, of which 10.2 billion barrels will be new water. By 1985, the total use requirement will be 92.8 billion barrels, of which 13.1 billion barrels will be new water.

Jan 1, 1966

By d&apos, Kathleen J. Amico

This summary appears in Minerals Year-book volumes I and III, which cover mineral production in the United States, its island possessions, the Canal Zone, and the Commonwealth of Puerto Rico, as well as the principal minerals imported into and exported from the United States. The several commodity and area chapters contain further details on production. A summary table comparing world and U.S. mineral production also is included. Mineral production may be measured at any of several stages of extraction and processing. The stage of measurement used in the chapter is normally what is termed "mine output." It usually refers to minerals in the form in which they are first extracted from the ground, but customarily includes for some minerals the product of auxiliary processing operations at or near mines.

Jan 1, 1966

By A. W. Deurbrouck

This report describes the preparation characteristics of the significant coalbeds from which samples could be obtained in Webster County, W. Va. In 1964, approximately 825,000 tons of coal was produced in the county, of which 732,000 tons was mechanically cleaned in three preparation plants. The Sewell coal bed accounted for 94 percent of the coal produced. Twelve samples were collected from five coalbeds. Four of the samples would require upgrading to meet metallurgical requirements; two others of just over 8.0 percent ash would require some upgrading. In general the coalbed samples collected in the county were of medium-sulfur and medium-to low-ash content as received or after removal of the sink 1.58-specific-gravity material.

Jan 1, 1966

By F. J. West

This paper deals with Jones & Laughlin Steel Corporation's new Adams mine, near Kirkland Lake, Ontario. After a brief discussion of ore structure, type, reserve tonnages, etc., the main body of the paper discusses the establishment of an open-pit limit based on economic considerations. The method used by J & L to arrive at an economically sound open-pit boundary its outlined fully. Physical limitations to open-pit boundaries are mentioned briefly. The paper concludes with a few remarks on the mining equipment in use and on its productivity

Jan 1, 1966

By R. E. Coleman

The molecular species occurring at the mineral-reagent interface of the galena-aqueous potassium ethyl xanthate system was studied by developing a technique for using an attenuated reflection method in conjunction with standard infrared spectroscopy procedures. Lead ethyl xanthate was detected from the infrared spectra of all galena surfaces treated in the pH range of 7 to 11. At pH 8.5, lead ethyl xanthate formed as a film chemically bonded to the galena surface. A solvent extraction sampling method was employed with infrared spectroscopy to obtain quantitative data on the lead ethyl xanthate removed from the galena surface. The data showed that between pH 7 and 11 thy quantity of lead ethyl xanthate physically adsorbed decreased as the pH was decreased; in the same pH range, the quantity of free lad ethyl xanthate in the aqueous medium remained constant, and the amount of unreacted xanthate varied.

Jan 1, 1966

By C. L. Klingman

The Bureau of Mines tested eight commercially available, activated charcoals experimentally to compare the following characteristics: capacity for adsorption of nitrogen at 77° K and 170 atmospheres' pressure, surface area, carbon tetrachloride adsorption capacity, hardness, and density. The nitrogen adsorption test was devised to simulate plant conditions occurring in the final step of purification in Bureau helium faciliti.es. The remaining tests were patterned after empirical acceptance tests that are widely used throughout the adsorbent industry. Surface area and carbon tetrachloride adsorption correlated well with nitrogen adsorption. The samples with low density generally had better adsorption qualities than those of higher density. The carbon tetrachloride test appeared to be the most practical for selecting a charcoal to be purchased, but an attrition, or hardness test should also be run to be sure the charcoal will not crumble in use.

Jan 1, 1966