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By A. M. Rowe

A considerable quantity of experimental hydrocarbon K-factor data has been correlated as a function of component identity, temperature, pressure and convergence pressure. To utilize these correlations effectively, convergence pressure must be determined accurately, particularly for volatile mixtures near their critical states. This paper presents phase diagrams that illustrate physically the meaning of convergence pressure. A new method, referred to hereafter as the "critical composition method", will be outlined for calculating convergence pressure. An example calculation has been included to illustrate how to use this new technique. INTRODUCTION The principle of hydrocarbon phase composition calculations as applied to such diverse problems as optimizing separator performance or predicting fluid compositions at various stages of reservoir depletion is the same. Usually, temperature, pressure and the numbers of moles of the various components of the fluid contained in a given volume are known. Questions answered by the phase calculation are what fraction of the total mass of fluid exists in each of the equilibrium phases, and what are the mole fractions of the various components in the two phases? To answer these questions the Natural Gasoline Supplymen's Assoc. (NGSMA) has correlated a considerable quantity of K-factor data as a function of temperature, pressure, component identity and convergence pressure.l To use these correlations to obtain the best answers possible, one must be able to calculate the convergence pressure. This is particularly true for over-all fluid compositions in the neighborhood of the critical state. STATEMENT OF THEORY Use of convergence pressure as a correlating parameter is based on a postulate similar to the law of corresponding states used in correlating PVT data of hydrocarbon gases. This postulate, which proposes convergence pressure as a correlating parameter, has been stated as follows: "The equilibrium vaporization constant for one component in a complex system is the same as the equilibrium constant at the same temperature and pressure for the same number or kind of components, providing only that the convergence pressures of the two systems are exactly the same at the same temperature and that the components are of the same homologous series".2 This law, as with all laws of physics, cannot be proven theoretically. It can only be justified by experimental data supporting its premises. Arguments have been made that this law violates Gibb's phase rule. For example, consider a four-component system. By Gibb's phase rule, which is thermodynamically rigorous, f = c — P + 2 =4, for a four-component, two-phase system. Thus, four independent intensive variables must be specified to establish completely all the intensive variables of the equilibrium phases. On the other hand, according to convergence pressure theory, only three variables need be specified for any mixture containing four different components. These variables are temperature, pressure and convergence pressure. Thus, the two laws appear to be in conflict. However, the convergence pressure postulate is more restrictive than Gibb's phase rule. It applies only to mixtures of the same homologous series. Hence, these two concepts are not in disagreement. PHASE DIAGRAMS DESCRIBING CONVERGENCE PRESSURE This paper presents phase diagrams grading from the simple two-component system to the more complex four-component system to illustrate convergence pressure. A less abstract definition of convergence pressure will be stated that is

George W. Maynard, New York, N. Y.:—It is well known that there are many magnetite-mines of which the ore is too low-grade for direct use in the blast-furnace. For carrying out the sintering process, the preliminary step, in the case of magnetites, is the separation of the ore from the gangue by magnetic concentration. The resulting fine-grain product is very objectionable in the blast-furnace, and when used must be a very small percentage of the charge. The sintering process has saved the situation by furnishing a product which is absolutely ideal on account of its cellular structure. (In reply to questions by W. J. Tudor, and Joseph W. Richards, the following additional information was given by Dr. Maynard.) The percentage of iron in the product is determined entirely by the degree of concentration of the raw material and is practically not increased by the sintering operation. The magnetic concentrates at Port Henry and at the Benson and one or two other mines contain from 65 to 67 per cent. of metallic iron. The cost of sintering is from 39 to 41 cents per ton of product, including superintendence, depreciation, and repairs. The itemized figures are about as follows : Mixing (including labor), 24; power, 9; ignition, 5; repairs, 3; total, 41 cents. Prof. J. W. Richards, South Bethlehem, Pa.:—From a metallurgical standpoint I question the accuracy of the statement on p. 374: " C.—An increased reducibility of the iron so treated. (This has been conservatively estimated as 5 per cent. better than the best available ore.)" It seems to me that when a material is' sintered in this way, the constituents present, as lime, silica, and alumina, have a chance to form a compound with the iron oxide; that such a compound, if formed before the material goes into the blast-

Jan 1, 1913

By Benjamin S. Lindsey, James Norman

BARITE (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some kinds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to 100 per cent through 325mesh. The crude rock with which all test work was done assayed 85.1 per cent BaSO4, 11.11 per cent Si02, and 2.85 per cent R2O3. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.1 The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of nonmetallic minerals in the presence of a large amount of slime is usually very difficult, and when done is an innovation calling for conditions different from those under which granular material is separated. LABORATORY FLOTATION WORK Preliminary investigation showed that the flotation reagents recommended by O'Meara and Coe1 for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1941

The Du Pont Magazine for August and September gives the following interesting information regarding recent progress in the use' of explosives. Blasting -Clay.-"The place where I tried blasting down clay for a brick yard had been worked for some years by old-time pick and shovel method. There was a large shallow pit, irregular in shape, with a perpendicular face at one end. I put down a line of holes 3 ft. deep and 6 ft. back from this face, loading each hole with one and one-half car-tridges of Red Cross Extra 40 per cent. dynamite. The charges were connected up to a blasting machine circuit and fired electrically. "Two of these shots kept the brick yard men very busy for two days taking out the loose clay. "I am convinced that if any brick yard man will try this method he will always have a blasting machine and dynamite on hand thereafter, because it cuts labor cost almost in two to get down the clay in. this way." In some clay pits the practice is to blast a large amount of clay in the fall, allowing it to freeze and thaw through the winter. Such clay is much easier to puddle in the spring than freshly dug or blasted clay. When the clay contains stones, the blasting loosens them and makes their separation-easy. Well-Drill Holes in Quarrying.-The well drill or cable drill method of working a quarry face is now in quite common use. The use of large drills is constantly increasing among quarrymen. In fact the growing tendency is for large machinery of all kinds such as mammoth crushers, steam shovels, etc. Volume is what is wanted nowadays. The advantages of the big drill over the piston driven drill are numerous. By carrying the holes the full depth of the face the stone is loaded and treated on one working floor. It eliminates the cost of bench cleaning. Loading operations are less frequent, thus lessening the danger. Stone can be shot down in greater volume and in better shape, making it economical to use a steam shovel. No bench cleaning makes it safer for the men. It is cheaper and can be used in outlying and temporary operations where the cost of installing a power plant would be out of the question. It permits a greater spacing of bore holes and eliminates the necessity of "squibbing" or springing. In this method usually holes from 4 in. to 6 in. in diameter are drilled the full depth of the face from 15 ft. to 2,0 ft. apart, and as far back and the whole face shot down at one time. The cost of well drilling may vary all the way from 20 cents to 75 cents: per foot, and in extremely hard rocks up to $1.50 per foot.

Jan 10, 1916

INTRODUCTION TO MINERAL INVENTORY The first explanations to be made must answer the questions: What is a mineral inventory, and how is a mineral inventory different from an ore reserve? The term mineral inventory is a relatively new designation-born of the computer age and grown to common usage with the development of computer techniques for extending drill-hole sample values to regularly gridded data blocks representing in situ mineral values. The term has been generally accepted by geologists and engineers because it has a precise meaning which avoids many of the ambiguities of ore reserve. A mineral inventory is an estimated inventory of mineral in place and is usually achieved by dividing the deposit into regularly spaced gridded blocks to which are assigned estimated values using various extension techniques. A mineral inventory makes no presumptions about the mineability of the blocks or their cutoff grade. Such parameters are implied with the use of the term ore reserve. Ore has a specific definition (see Chapter 1) and ore reserve must reflect that definition and thus has economic and mining constraints. An ore reserve will be different under different economic and mining conditions and is subject to reclassification by many factors. The term mineral inventory avoids all such ambiguities. A mineral inventory estimate may be good or poor according to how much is known about the deposit, how extensively it has been sampled, and what techniques have been employed to assign estimated grade to the blocks. Such an inventory, however, does not change with time, economic conditions, or mining technology, but only with new and better data and methods. Thus, the mineral inventory is an excellent designation for describing mineral value distribution within a deposit's geological setting. The techniques for assigning values and tonnage to mineral blocks or panels are the subjects of this chapter. Whether a summation of the blocks be called a mineral inventory or mineral reserve is not important. Many conventional methods for computing reserves of minerals refer to the methods in terms of ore reserve calculations. OBJECTIVES OF MINERAL INVENTORY OR RESERVES Mineral inventories are computed for the purpose of determining the quantity, the quality or value, and the spatial distribution of potentially economic minerals within the earth. Such computations are made at all stages in the life of a mineral extraction process, from the early exploration phase to the final year in the life of a mine. To quote Popoff (1966, p. 2), "They are the most responsible and irreplaceable tasks in the valuation of a mineral deposit. Efficiency in extraction and productiveness is impossible without accurate reserve computations." The accuracy of estimate required for each of the three parameters of quantity, value, and location is dependent upon the objective for which the reserve estimate is being made. Again quoting Popoff (1966, p. 2): Reserves are computed to determine the extent of exploration and development; distribution of values; annual output; probable and possible productive life of the mine; method of extraction and plan design; improvements in extraction, treatment, and processing; and requirements for capital, equipment, labor, power, and materials. Such computations are used to assist development

Jan 1, 1980

By J. J. Strohl, H. J. Schwellenbach

This paper relates the results obtained by decreasing the size of feed to a rod mill screen circuit. As would be expected, added production was gained and a finer grind with no tonnage loss was made possible. THE MacIntyre mill of the National Lead Co. has four parallel sections in which magnetic and gravity separations are made. Ore from a 5000-ton bin is fed by Hardinge constant weight feeders to a 6x12-ft open-end Marcy rod mill in each section. Rod mill discharge is bucket elevated to two 4x10-ft Tyrock screens whose oversize is returned to the rod mill. Screen undersize is pumped to Crockett separators for magnetite removal, and the Crockett tailings are sized and tabled to make an ilmenite concentrate. Minus 200-mesh material, overflowed by the Crockett and Dorrco sizers is thickened, de-slimed, and concentrated by flotation.' By 1948, the development of a successful slime flotation process and numerous improvements in the gravity circuit of the mill had increased the capacity of the available concentrating equipment. At the same time, improvements in the operating techniques of the dry crushing plant and improved feeding of the crusher by the mining department had appreciably increased the production rate per operating hour in that plant. Therefore, it was decided to take advantage of the added crusher capacity to produce a finer rod mill feed and in that way increase grinding capacity. At approximately the same time, finer screens were installed in the rod mill circuits to give finer grind and thus improve liberation of the magnetite and ilmenite from the gangue and from one another. Prior to the first part of 1948, a 3/4-in. limiting screen was used for sizing rod mill feed. The first reduction in crushing plant screen size was to 1/2 in. With this screen, the circulating load in the tertiary crushing circuit was too high and plant capacity dropped below a practical hourly rate. A 9/16-in.-sq opening screen, installed next, proved satisfac-

Jan 1, 1951

By H. J. Schwellenbach, J. J. Strohl

This paper relates the results obtained by decreasing the size of feed to a rod mill screen circuit. As would be expected, added production was gained and a finer grind with no tonnage loss was made possible. THE MacIntyre mill of the National Lead Co. has four parallel sections in which magnetic and gravity separations are made. Ore from a 5000-ton bin is fed by Hardinge constant weight feeders to a 6x12-ft open-end Marcy rod mill in each section. Rod mill discharge is bucket elevated to two 4x10-ft Tyrock screens whose oversize is returned to the rod mill. Screen undersize is pumped to Crockett separators for magnetite removal, and the Crockett tailings are sized and tabled to make an ilmenite concentrate. Minus 200-mesh material, overflowed by the Crockett and Dorrco sizers is thickened, de-slimed, and concentrated by flotation.' By 1948, the development of a successful slime flotation process and numerous improvements in the gravity circuit of the mill had increased the capacity of the available concentrating equipment. At the same time, improvements in the operating techniques of the dry crushing plant and improved feeding of the crusher by the mining department had appreciably increased the production rate per operating hour in that plant. Therefore, it was decided to take advantage of the added crusher capacity to produce a finer rod mill feed and in that way increase grinding capacity. At approximately the same time, finer screens were installed in the rod mill circuits to give finer grind and thus improve liberation of the magnetite and ilmenite from the gangue and from one another. Prior to the first part of 1948, a 3/4-in. limiting screen was used for sizing rod mill feed. The first reduction in crushing plant screen size was to 1/2 in. With this screen, the circulating load in the tertiary crushing circuit was too high and plant capacity dropped below a practical hourly rate. A 9/16-in.-sq opening screen, installed next, proved satisfac-

Jan 1, 1951

G. SHERBURNE LAGERS (written discussion*).-Mr. Kennedy's discussion1 of Mr. Matteson's paper takes the form of a criticism of my own comments2 on this paper. Mr. Kennedy is a respected authority on matters pertaining to the salt-dome oil fields, and his characterization of my "elaborate figures" as "worthless" is sufficiently candid and comprehensive to warrant a brief reply. My "voluminous figures" consisted simply of a rough estimate of the minimum quantity of salt in the Humble dome, and a calculation of the volume of sea water and of the volume of saturated brine which this salt would represent. Mr. Kennedy apparently interprets my remarks as opposing the idea that so large a volume of salt could have been deposited from sea water, for lie cites the area and thickness of European salt beds; but nothing was further from my intention. Given an arm of the sea, an arid climate, and evaporation under a hot sun, it is easy to conceive the formation: of almost any thickness of bedded salt. I cited the figures in connection with Harris' theory of the origin of salt domes, according to which the plugs were formed by the deposition of salt from ascending brine solutions, owing to the drop in temperature as they neared the surface. I pointed out the well-known fact that the solubility of salt is only slightly affected by temperature, and that a drop of 80° C. would cause the deposition of less than one-tenth of the salt in solution; hence that more than ten times the volume of salt actually forming the plug must have been involved. If ten times the salt actually in sight be computed in terms of brine and multiplied by 50 or 60 to take into account all of the known salt domes, the resulting figure is so enormous that I am not at all as sure as Mr. Kennedy seems to be that the porous stratified rocks of eastern Texas and western Louisiana could contain or furnish so great a volume of migratory brine.

Jan 8, 1918

By K. L. Meissner

IT is well known that the so-called pure aluminum contains noticeable amounts of impurities, chiefly iron and silicon, and many investigators have studied the forms in which these impurities exist. Hanson and Archbutt1 state that iron exists in aluminum as FeAl3 and silicon as elementary Si. The solubility of FeAl3 in solid aluminum is practically zero, or at, least so small that the smallest trace of this compound is always visible as a separate constituent. Under the microscope an untrained eye can hardly distinguish, without etching, the two constituents FeAl3 and Si, but they can be differentiated by suitable etching reagents. Anderson2 also found the same results. At the same time, Merica, Waltenberg, and Freeman3 found a constituent of unknown composition. They found a small thermal effect, at 610° C., on the cooling curves of aluminum with small amounts of iron and silicon. The intensity of this effect increased with increasing silicon content, until an effect occured at 576° C. due to the eutectic between aluminum and silicon. The authors ascribed the effect at 610° C. to a compound, which they call "X constituent." It was thought to be a ternary compound containing iron and silicon and could be observed under the microscope as dark particles. Dix4 has published unetched photomicrographs of an aluminum with 0.51 per cent. iron, 0.99 per cent. silicon, and 0.32 per cent. copper that shows three constituents: the dark Si (black in the figure), the lighter FeAl3, which appears in half tone and crystallizes in needles, and a constituent of the same color as FeAl3 but of different crystal form, often resembling Chinese script. This last constituent, Dix thought, is a compound of Fe and Si; not the compound FeSi but a compound containing a relatively small amount of silicon. Therefore an alloy of aluminum, iron, and silicon (the copper should not be regarded in the following considerations) must contain the following four constituents: Al, FeAl3,

Jan 1, 1926

By J. B. Mackintosh

THE present note is intended as an addition to my previous communication on the volumetric determination of manganese, read at the Roanoke meeting," it having been suggested that the circumstances under which my experiments had been conducted, were essentially different from those met with in the analysis of irons. The method used in these experiments is the same in all its details as that described in the paper referred to. I have made seven experiments in all: two of these were in duplicate on half a gramme of a sample of spiegel dissolved in hydrochloric acid; one was on the same amount of spiegel with the addition of 25 C.C. of a standard solution of potassium permanganate; one was on the same amount of spiegel with the addition of 35 C.C. permanganate and much organic matter, viz., one drop of castor-oil, two or three drops of coal-tar benzol arid of gasolene (petroleum), about ten of alcohol, portions of starch and of sugar about the size of a small pea, and about half an inch of a common match cut into shavings. This organic matter was added to the manganese solution after the hydrochloric acid had been replaced by nitric, and the solution was heated until the wood-shavings had disappeared. The fifth experiment was made by dissolving half a gramme of spiegel alone in nitric acid; the sixth by dissolving half a gramme of spiegel in nitric acid with the addition of 25 C.C. potassium permanganate, some oxalic acid, half an inch of a match, one filter-paper 7 cm. in diameter, and two drops each of castor-oil and turpentine; and the seventh experiment by dissolving half a gramme of spiegel in hydrochloric acid and adding 35 C.C. permanganate, without however taking the precaution to evaporate off all the excess of hydrochloric acid. Under these circumstances, one would expect that if organic matter exercises any influence on the determination, it would be plainly evident in the results obtained. But the accompanying table of results

Jan 1, 1885

By H. J. Wasson

With the close of 1932 and the third year of the depression, the activity of oil production presents, amidst the general wreckage and chaos of industrial society, a somewhat unique picture of rationalized economic effort. How long it will continue to present such a picture, however, is a subject for conflicting surmises. East Texas still dominates the contemporary horizon, but it has become, at least for the time being, a definitely known factor. With its 9500 wells it is approximately 90 per cent drilled up. So long as production control obtains, it is merely one important factor of the national oil reserve. Domestic Production The notable new discoveries in the United States were less numerous than for several years. Elsewhere in the world the record is much the same. The Conroe field in Montgomery County, Texas, lying in an intermediate zone that might be classified either as Gulf Coast or East Texas, represents perhaps the single example of a truly major discovery during the year. Elsewhere in Texas the new pool discoveries, about a dozen or so in number, were nearly all in the region known as Southwest Texas. Oklahoma contributed seven or eight new pools of the routine "run-of-mine" caliber, and the opening up of a few deeper oil pays also were of some significance. Continued expansion of the proved and semiproved reserves in Kansas added an important increment to the oil resources of that state. In California not a single new field was added to the roster, though deeper pay zones equivalent to or of greater importance than many new fields in other parts of the country were discovered or indicated. The new deep zone in the Belridge field is considered by some to underlie the prolific Temblor and may thus forecast the widespread distribution of a potentinl oil horizon underlying many San Joaquin Valley fields below the depths thus far exploited. Aside from the routine operations in connection with settled production, the Eastern fields were decidedly inactive. Further new develop-

Jan 1, 1933

By J. Walter Scott

IT is usual practice in the copper industry to use open horizontal molds for casting tough-pitch copper wire bars.1 A wire bar cast in this manner is partly characterized, by heavy wrinkles and a comparatively deep skin of oxide on the top of the bar, corresponding to the open side of the mold. On the theory that the rough, high-oxide surface might have an adverse effect on the rolling and drawing properties of a wire bar and might account for some of the irregularities of mill behavior, several bars which had been planed to remove the wrinkled surface were processed into wire. These bars responded to mill treatment more satisfactorily than did the regular wire bars. Realizing that machining the surface of one face of each bar would not be commercially feasible, it was decided that casting the metal into a vertical mold and cropping off the pouring end would accomplish. approximately the same result. Several wire bars of commercial size (250 lb.) were so cast and processed into wire for comparative test with bars cast in the usual horizontal molds. It is the purpose of this paper to present the results obtained from this investigation, in which commercial bar sizes and processing technique were used throughout. The results show that in general copper wire bars cast vertically are superior to those cast horizontally.

Jan 1, 1930

Restrictions on the use of zinc will be a thing off the past in a few months. Government allocations on the metal are also expected to go by the board. Concurrently, action is also expected in reference to lead allocations. Government stockpile goals for zinc have been reached. The International Union of Mine, Mill and Smelter Workers lent support to United Steel Worker demands and at the same time put in their own bid for a 25-cent an hour increase at a meeting held in Denver. While backing the USW, the IUMMSW charged the Steel Workers with membership raiding. Iron and steel companies producing about 92 pct of steel ingots in the United States, showed nearly a 13 pct decline in net profit during 1951, compared with the previous year, despite a 22 pct increase in their combined revenue. Federal income tax rose 61 pct, to more than 012 million. New iron ore reserves are being sought in Canada by Jones & Laughlin Steel Core, The company has acquired exploration options near Petersborough on the north shore of Lake Ontario in Durham, Northumberland and Frontenac Counties. *'A fourth property is southwest of Ottawa, in the Kingston, Ontario area..

Jan 1, 1952

By Robert Stefanko

Shortwall mining represents a compromise between the room-and-pillar and longwall systems. Figure 1 shows that the shortwall layout is very similar to that for longwall panels, the primary difference being that the shortwall is generally 150 to 200 feet wide while longwalls are 350 to 600 feet wide. The development of entries is divorced from the production of the walls with both systems. However, the depth of the web is considerably different in the shortwall system. Because a standard continuous miner is employed, a depth of 10 feet is normally mined on a single pass. This greater web thickness requires the use of a specially constructed support that can support the much longer cantilever bar that must extend over the working area. This is accomplished by not only increasing the length of the bar but also strengthening it structurally; however, the key to success lies in articulating the cantilever from the base and supporting it with a short hydraulic jack leg. This arrangement provides the additional strength required in the support. It should be apparent that a shortwall support is more costly than the type used for longwall.

Jan 1, 1981

By Sidney Wise

WHILE the installation of mine bulkheads to retain water under high pressure is y no means a rarity, the following points Which arose in the designing and placing of two of these bulkheads may be of interest: The Hibernia magnetite mine, located about 40 miles west of New York, in the State-of New Jersey, is partly filled with water. This mine is located on an ore lens, the outcrop of which is over a mile long. The ore has been mined from this lens from the surface to a depth of more than 1,500 ft. It was held desirable to- separate the old workings from the new, and to allow the former to fill to the 850-ft. level. Two weak places existed between the new and old workings below this level: namely, a temporary bulkhead on the 10th level and a rock bulkhead of indeterminate thickness on the 16th level. When the matter of allowing the old workings to fill was investigated, the fact was developed that if these old workings were filled, the bulkhead on the 10th level would be subjected to a water pressure of about 50 lb. per square inch, and that 200 lb. per square inch would act on the 16th-level bulkhead. As the above-mentioned barriers were not deemed of sufficient strength to permit of these pressures, it became necessary to design and install new bulkheads. Design As the 16th-level bulkhead was required to withstand a pressure of 200 lb. per square inch, it presented some difficulties. A careful consideration of the various types of mine dams now in use led to the adoption of a design of the form of a truncated wedge. In this, the pressure side of the dam is of greater area than the back, so that the resultant action is similar to driving the wedge. By cutting generous skewbacks in the walls, roof, and floor, this type in reality becomes an invisible arch. The wedge feature tends to compress the materials in the bulkhead, thereby adding to its imperviousness.

Jan 8, 1914

By J. H. Hamilton, J. R. Lewis, J. H. Dismant, W. M. Fassell

RECENTLY this laboratory undertook the task of preparing some low carbon metallic cobalt by the carbon reduction of precipitated cobalt oxides. The oxides came in two lots and had the compositions given in Table I. Industrially, cobalt rondels' are made by the carbon reduction of cobalt oxide in small reverberatory furnaces at temperatures near but not above 1050 °C. This is a slow and tedious small batch process but does give cobalt metal which is low in carbon (1 pct C). Inasmuch as these cobalt oxides were relatively low in copper and iron it was decided to reduce them with petroleum carbon in a small three-phase electric arc furnace of about 3 to 5 Ib of metal capacity. It was hoped such a procedure would save considerable time and perhaps also indicate an improved commercially feasible process. The furnace was preheated by using small pieces of carbon electrodes to maintain the arc until a temperature of 1500°C was reached. The broken pieces of electrodes were then removed and 500 g of the cobalt oxides and 60 to 100 g of petroleum coke added. At the end of the reduction reaction, a high lime flux was added to the furnace to facilitate the removal of sulphur. Due to the fineness of the cobalt oxide powder used and also to the presence of chlorides there was considerable dust lost in charging the furnace. This was overcome by preparing briquettes composed of the cobalt oxides, charcoal, and a little bentonite to serve as a binder. The results obtained are summarized in Table 11, which shows that the cobalt metal produced in the arc furnace was high in carbon varying from 2.5 to 3.5 pct. This, of course, is much too high. For certain uses, such as in the preparation of permanent magnets, the carbon content of cobalt must be low. It was necessary therefore to find an effective method of reducing the carbon content of the cobalt that had been prepared in the arc furnace. Van Arkel3 recommends the use of Co2O3 as a means of removing carbon from cobalt. Experiments by the authors indicate that carbon is removed with difficulty by this method. Other methods used, including lancing of the molten high carbon cobalt with a jet of oxygen, proved to be ineffective. The method finally used makes use of the fact that cobalt metal is decarburized by carbon dioxide at the temperature of the molten metal. Two methods were used: 1—carbon dioxide was bubbled up through the molten cobalt, and 2— molten cobalt was maintained in a carbon dioxide atmosphere. In the first method the gas was introduced below the surface of the molten metal by means of a quartz tube. A high frequency induction furnace was used to keep the cobalt molten in both of these experiments. This kept the metal somewhat agitated and no doubt was an important factor in hastening the decarburization 'process by the second method. Both methods gave satisfactory results as shown in Table 111. An interesting observation in connection with this 'work was that a small sample of carburized cobalt metal could be decarburized by heating it with an acetylene torch adjusted to give an oxidizing flame. This may have been due to the presence of carbon dioxide in the products of combustion. Samples of molten high carbon steel were decarburized by the same method and it is suggested that nickel and perhaps manganese can be decarburized in a similar manner. Additional work, including rate studies and other theoretical aspects of this problem, is in progress in this laboratory.

Jan 1, 1953

By John B. Campbell, George G. Binder, Loren H. Jenks

Conventional methods of producing crude oil generally leave in the depleted reservoir 1 to 3 bbl of oil for every barrel brought to the surface. This paper describes a field test which explores the possibility of using gas-driven liquid propane to improve oil recovery efficiency. Laboratory theoretical and experimental studies leading to the field test indicated that low residual oil values could be obtained using limited amounts of propane driven by gas. The field test involved (I) repressuring the reservoir to the vapor pressure of liquid propane, (2) injecting the liquid propane, and (3) injecting dry natural gas to drive the propane and oil to the producing wells. Considerable preliminary work, including new drilling, work-overs, and a pressure survey was necessary. During the test, oil production rates have averaged about nine times the final primary rates. The field average GOR is still below the pre-test value. Oil recovery to date is 112,000 STB. About one-third of the 143,-000 bbl of propane injected has been produced to date. Results of the C-2 block test are encouraging and larger, more definitive field projects ore indicated. INTRODUCTION The cost of finding new crude oil reservoirs continues to increase. Today the oil industry is drilling more and deeper wells and making fewer big discoveries. Nevertheless, the demand for oil and oil products increases each year. It is natural that oil companies, faced with this situation, concentrate on recovering more of the oil existing in our known crude oil reservoirs. There is room for much improvement. For every barrel of oil brought to the surface by present day methods of producing crude oil, generally 1 to 3 bbl are left behind in the depleted reservoirs. The "unrecoverable" oil in petroleum reservoirs is largely "trapped" by capillarity. Since flushing with a solvent is exceedingly effective in combatting oil loss due to capillarity, much effort in this direction has been made in recent years1,2,3,4,5. Liquefied petroleum gas (LPG) has been suggested as a relatively inexpensive. abundant, easily recoverable solvent for crude. Some operators have observed striking responses in oil recovery at production wells offsetting input wells in LPG storage reservoirs6,7,8. In spite of the low unit cost of LPG, however, it is uneconomic in general to inject a volume of LPG into a reservoir to remove a like volume of oil. A modification of solvent flushing in which a limited quantity of liquid propane is gas driven through a reservoir appears capable of recovering much more than 1 bbl of oil per barrel of propane injected. Also, most of the propane injected should be recoverable for sale or re-use. Since such a process could well have widespread and profitable application, The Carter Oil Co. is making an extensive evaluation of the technique's possibilities. Laboratory development of the gas-driven propane recovery technique was sufficiently encouraging to justify testing in the field. Since 1952, the Production and Research Departments of The Carter Oil Co. have cooperated in a field test in the C-2 Block leases of the

Jan 1, 1958

By Charles C. Hawes

DETERMINATION OF SILICA OXIDE iron ores usually are found in intimate association with silica and phosphorus compounds. Their quantitative separation and purification sometimes present difficult problems to the chemist. Silicic acids may represent various degrees of dehydration. They are exceedingly weak, but combine with metallic acids and form some of the most stable oxides in nature, the silicates. When iron ores are treated with hydrochloric acid, they yield practically all their iron. However, apart from rare exceptions, varying amounts of insoluble residues of silica, alumina, lime, magnesia and compounds of phosphorus, sulphur, titanium, chromium and others will be left. If the oxides of silicon, aluminum and titanium are present in small quantities, the insoluble residue is generally very small, but the presence of these oxides more usual in larger quantities. Therefore, only a special treatment can break the bond between these elements. Ore Residues Acids remove the soluble constituent of the ore, leaving the insoluble residue, which chemically is rock or gangue and must be treated accordingly. Alkali carbonates are used frequently to break up the residue, but other fluxes have also been recommended, such as a number of lead and boron salts. The introduction of these salts, which offers certain advantages, requires, however, their removal before the other constituents can be analyzed, and this elimination is sometimes difficult. Usually in quantitative analysis silicates are dissociated by fusing them in a platinum crucible with sodium carbonate, thereby forming sodium silicate, Na2SiO3, sodium aluminate, Na2A1204, sodium titanate, Na2TiOs, and carbonates of other elements. All the carbonates are soluble in hydrochloric acid, but also some silicic acid is formed that must be rendered insoluble. To this end the solution is evaporated several times, as the first evaporation still leaves as much as 5 per cent of the silica soluble. Even after a number of evaporations, minute quantities of silica may be found with the iron and alumina present. Perchloric Acid as an Agent for Dehydrating Silicic Acid Perchloric acid, HCI04, (60 per cent), has been used for years as a solvent, but few chemists have used it to dehydrate silica. It is derived from anhydrous perchloric C1207, which is most unstable and dangerous. Perchloric acid is a strong oxidizing agent, which boils at 203°C. It is more effective in rendering silica insoluble than any other known agent, and most rapid in action. After perchloric acid is added to a mixture containing silicic acid, the resultant solution is

Jan 1, 1945

By P. K. Foster, A. McNabb

A consideration of the literature shows the inadequacy of Fick's Laws to describe the diffusion of hydrogen in steels below 400°C. These laws are modified an the assumption that hydrogen is delayed at fixed sites in the lattice. Approximate and exact solutions of the resulting nonlinear system are derived for simple geometrical shapes. The results qualitatively account for the observed anomalous behavior. Experimental methods for verifying the theory are suggested. 1 HIS paper presents a new analysis of the diffusion behavior of hydrogen in steel based on a physical model which supposes that hydrogen atoms wander in a random manner through the crystal lattice, but tend to get trapped or delayed at certain fixed sites uniformly distributed throughout the metal. These sites, which will be called traps, are regarded merely as potential wells of significantly greater depth than those encountered in regular regions of the crystal lattices and no assumptions are made concerning their nature or origin. The results of experimental studies of the diffusion of hydrogen in iron and steel have usually been reported in the literature in terms of a diffusion constant D derived under the assumptions that the hydrogen concentration C is governed by Fick's laws.1 Fig. I is a composite of published graphs of the man. ner in which the values of D, so derived, vary with temperature. It is convenient to consider this material in two categories; the high temperature results above 400°C, and the results at lower temperatures. The graphs 2, 3, 4, 5 in the first class lie within a factor of three of each other and are relatively consistent compared with the low-temperature values. There is an increasing divergence in values of D with decreasing temperature till at room temperature they are spread over three orders of magnitude. Small values of D have been obtained for work-hardened specimens.' It is evident that D is a function of other variables besides temperature in this range and that these neglected variables are in some way connected with the work hardening experienced by the specimen. In view of evidence for an interaction between hydrogen in solution and dislocations9'10 and adsorption on crack surfaces,' some doubts must be entertained about the validity of Fick's laws and their associated physical model of noninteracting particles in random motion through the medium. More direct evidence of their inapplicability to the diffusion of hydrogen in steel was first produced by Darken and smith." Consider the permeation of hydrogen through a plate of thickness a under a boundary concentration Co at the ingoing, and zero at the outgoing, face. If Fick's first law1 is valid, the steady state flux P, through unit area is DCo/a. In addition, the concentration C varies linearly throughout and Qo, the mean quantity of hydrogen in the medium, is co/2. Compare Qo with Q1 the mean quantity required to saturate the same specimen to a uniform concentration G. In this case Ql = Co and hence the ratio

Jan 1, 1963

By F. W. Jessen, C. A. Johnson

The effect of treatment with ferrochrome lignosul-fonate on both sodium and calcium bentonites has been examined. In the early stages of treatment it appears that some base exchange of iron and chromium for sodium may occur with the sodium bentonite. Such exchange appears specific for exchange of sodium ions when the calcium ion concentration represents 40-5.5 per cent of the total exchangeable cations, and when additions of lignosulfonate are less than 1 lb per bbl. Adsorption appears entirely physical above 1 lb per bbl treatment level for all concentrations of calcium studied. Gel strength and plastic viscosity of both calcium and sodium bentonite systems were reduced with treatments of ferrochrome lignosulfonate up to 2 Ib per bbl, the greatest reduction occurring within a range of calcium concentration of 40-5.5 per cent of the total exchange capacity of the clay. INTRODUCTION The problem of control of viscosity and gel strength of drilling fluids by the action of thinners or dispersants has been studied by many investigators.1-7 In addition, much work has been done on formation of gel structure in clay suspensions. However, gel formation and structure still are incompletely understood, and the use of the various dispersing chemicals is based, to a large extent, on data almost entirely empirical in nature. In recent years the lignosulfonates have become increasingly important in the treatment and control of drilling fluids. More specifically, ferrochrome lignosulfonate has found rather wide acceptance, particularly in calcium systems.5-7 Lignosulfonates are refined lignin products made from spent sulfite liquor from which the fermentable sugars have been removed.15 The exact structure of lignin is not known; however, it is believed to be a phenolic propane type polymer which may exist as a branched chain or cross linked structure. The molecular weights of lignosulfonates probably range from 300 to 100,000 or more.15 A better understanding of the mechanism of adsorption of dispersants is essential before improvement and development of characteristics of drilling fluids and drilling fluid control is possible. This investigation was undertaken to determine the action of ferrochrome lignosulfonate on sodium and calcium montmOrillonite' LABORATORY INVESTIGATION A Stormer viscosimeter and Fann V-G meter were used to measure viscosity and gel strength. A Zeiss spectrophotometer was used for analysis of Fe and Cr and the flame attachment was employed in the analysis of Na, Ca and Mg. A General Electric X-ray diffraction unit utilizing Copper Ka radiation and a Ni-filter was utilized in the X-ray studies. PROCEDURE Two systems were studied. Predominately sodium clay, obtained from Wyoming, and a predominately calcium clay from Texas were used. These particular samples were chosen because of the extensive work of characterization completed by Mungan. Ionic base exchange capacity determined by flame photometry and total exchange capacity by the Kjehldahl method were obtained experimentally. A 7-per cent suspension of the sodium clay and a 20-per cent suspension of the calcium clay in distilled water were prepared by mixing with a high-speed mixer. The suspensions were allowed to stand for two weeks for complete hydration. Calcium chloride was added to portions of the sodium and calcium cla suspensions to obtain suspensions varying in Ca++ concentration as shown in Table I. A series of treatments was run with 500-ml portions of the original suspensions using a ferrochrome lignosulfonate. Treatment was carried out in the same way with each of the suspensions of varying Ca concentration. Viscosity and gel strength were measured and a filtrate obtained at each treatment level. Ten ml of filtrate were diluted to 50 ml, and aliquot portions of the 50 ml were taken for the Na, Ca, and Mg analysis by the flame photometer. The pH of these filtrates ranged from 7 to 7.3. Standard