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By F. S. Crawford

IRON and copper are mined in the Lake Superior district. The iron mines of the district have the best safety record for that industry in the country as a whole, while the copper mines of the district rank second in two of the four years recorded (Table 1). In Utah copper comes mainly from open-pit mines, which enables that state to lead easily in safety. All of the Michigan production comes from deep underground workings. About 60 per cent of the iron miners in St. Louis County, Minnesota, are employed at open-pit mines; this favorably affects the combined open-pit and underground accident-frequency rate, as this county provides most of the Minnesota-mined iron ore. In Michigan, however, there are few open-pit mines, the bulk of the production coming from underground mines, while all of the Wisconsin production, just across the state line from Michigan, is from underground mines. In spite of the fact that fewer mines in Michigan use the safer open-pit method, the iron-mining industry of that state maintained a consistently low record from 1931 to 1934; however, it was many points behind its nearest competitor, Minnesota, with its much greater production from open-pit mines.

Jan 1, 1939

By W. W. Stephens, W. J. Kroll, H. P. Holmes

THE only two methods for producing commercial quantities of malleable zirconium, up to now, have been using magnesium reduction of the anhydrous chloride under a neutral gas, and using purification of raw zirconium by the iodide dissociation method on a hot filament. The purity of the metal obtained by the latter process is about the same as that resulting from the chloride reduction, with the exception of the oxygen content, which may be about 0.05 pct lower in the iodide metal. Even traces of oxygen have a strong hardening effect on zirconium. Since, in the iodide process, the impurities, Si, Al, Fe, Ni, and Mg in the raw zirconium used, are carried over, it would appear uneconomical to use this method of refining solely to eliminate the traces of oxygen, unless very soft metal is desired. One important step to improve the iodide method, namely, dissociating pure iodide made from carbide and recycling the iodine, which would change this refining process into a method for extracting zirconium from the ore, has not yet been made. The Bureau of Mines, by using the chloride reduction, wanted to produce quantities of a reasonably pure and malleable metal at low cost for large-scale industrial use. This aim has been achieved, and a pilot plant permitting production of 600 lb of malleable zirconium per week will be described (fig. 1). Briefly, the Bureau of Mines process consists of reducing purified gaseous anhydrous zirconium chloride with fused magnesium under a noble-gas atmosphere. The reaction product, magnesium chloride, and any excess magnesium metal present are removed from the sponge zirconium in the next step by fusion and evaporation in a good vacuum at about 925°C. In this process, care is taken to keep air out of contact with the hot metal, which otherwise would contaminate the product with oxygen and nitrogen. Both these impurities embrittle zirconium even when present in an amount as low as 0.1 pct. A number of previous reports1-3 describe the method and the various improvements that finally led to a workable process. The major steps made were the production of large quantities of carbide, which is the raw material for producing the chloride, its chlorination with reasonable efficiencies, and the elimination of iron trichloride contained in the raw chloride, as well as that of the zirconium oxide which is always present in this product. The physical nature of the anhydrous chloride, which sublimes at 331°C at atmospheric pressure and melts at 420°C under a pressure of 25 atm, made it necessary to provide a special safety device on the purification and reduction vessels in the form of a lead-alloy seal, permitting escape of excess gases if pressure tended to build up. The main difficulties encountered in the reduction and in the following step, salt separation in a vacuum at elevated temperature, were caused by the material from which the reaction pot was constructed—iron. This metal reacts with zirconium at about 940°C with formation of a eutectic. The last step, salt separation by evaporation of the magnesium and magnesium chloride in a vacuum, is quite unconventional and has not been used before on such a scale. It is only due to the improved construction of high-vacuum pumps, especially oil-diffusion pumps, that such a method could be used. The various steps of the Bureau of Mines process, as described in the general outline above, may be summarized as follows: (1) production of the carbide, (2) chlorination of the carbide, (3) purification of the raw chloride, (4) reduction of the pure chloride with fused magnesium, (5) separation of excess magnesium and magnesium chloride in vacuum at elevated temperature, and (6) melting of the sponge obtained. Production of Carbide The arc furnace, described in a previous report,' was improved both to reduce the graphite consumption caused by the burning of the bottom plates and to concentrate the heat in order to obtain better power efficiency. This was achieved by providing the bottom with graphite plates entirely embedded in refractory bricks, the contact with the current being made with three water-cooled copper plugs. Figs. 2 and 3 show the arrangement. The crucible, made

Jan 1, 1951

By Ford R. Bryan, Edward F. Runge

BECAUSE of the need for ductile heat resistant alloys of non-strategic composition, there has been metallurgical development of Fe-A1 alloys possessing improved ductility and hot strength, together with high oxidation resistance. Iron and alu- minum form solid solutions up to approximately 35 pct Al. Alloys in the 8 to 12 pct A1 range are characterized by excellent oxidation resistance, high electrical resistivity' and, when appropriately alloyed, have creep rupture strength equivalent to that of the austenitic stainless steels.' At higher aluminum levels, the magnetic properties are of considerable interest. Nachman and Buehler" have recently reported on the desirable magnetic characteristics of the 16 pct alloy.

Jan 1, 1957

By William Fink

MANY investigators have attempted to determine the true nature of the internal changes taking place during aging. Merica, Waltenberg and Scott1 were the first to propose a theory of age-hardening. They attributed the age-hardening of duralumin to the precipitation of minute particles of the compound CuA12. Later Zay Jeffries and R. S. Archer2 augmented the above theory by suggesting that the small CuA12 particles acted as "keys" causing "slip interference." Many other investi-gators3 have devoted much time to the mechanism of age-hardening, some corroborating the "precipitation" and "slip interference" theory, others coming to different conclusions because of effects that to them seemed unexplainable by the early theories; e.g., the increase of electrical resistance upon aging, the fact that no change in lattice parameter could be detected during the early stages of aging even at elevated tempera-tures, and the fact that the density did not change as would be predicted. In 1932, Merica revised4 his earlier precipitation theory to take care of these presumably anomalous effects. This revised theory, the "knot" theory, assumes that substantial age-hardening occurs before actual precipitation of solute as discrete particles. The assumed mechanism is one of diffusion of solute atones into groups forming distorted regions which act as "hard" spots and cause slip interference. These "knots" are assumed to have approximately the same lattice arrangement as the solvent.

Jan 1, 1936

By P. G. Beckett

THE problem of handling the large quantities of water encountered in the Old Dominion mine presents many features of interest. In the present paper are discussed the probable sources of water, the pumping equipment, the increased flow into the mine in the early part of 1915, culminating in the flooding of the 18th and 16th levels in March of that year, and the difficulties that were met with during the high-water period. I. PRELIMINARY The Old Dominion mine, situated 1 mile north of the town of Globe, Ariz., has long been one of the prominent copper producers of the State, and until the opening up of the copper schist deposits in the neighboring mines of Miami, was responsible for the greater part of the copper output from the Globe district. As the gradual exhaustion of its orebodies near the surface led to the downward development of the mine, more water was encountered in the western portions directly underlying the dacite formation until the drainage problem became a serious factor in the operation of the mine and in the economical extraction of the ore. A heavy inrush of water on the 10th level of the mine in 1906, preceded by still earlier water difficulties, rendered imperative the immediate installation of a pumping equipment capable of handling large flows of water. While the Old Dominion has been recognized as a wet mine since its early clays and one in which the complete control of the water situation was of paramount importance in the development of the lower levels, it is chiefly in the last nine years, since the installation of the increased pumping equipment, that the mine has developed and handled large quantities of water.

Jan 4, 1916

By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962

By Henry Ferguson

THIS paper is a preliminary statement, intended to present the more important results of the recent studies of the ore deposits of the Alleghany district in advance of the publication of the complete report, now in preparation. The Alleghany district (Fig. 1) has been a producer of gold since the early days of California gold mining. As in other California gold camps, placers yielded the bulk of the earlier production, but during the last 30 years lode deposits have been the only important source of output. The district differs from other California gold-quartz districts in that nearly all the production is from small shoots of high-grade ore. The mining camps of Alleghany and Forest are on the western flank of the Sierra Nevada range about 20 miles west of the crest. The gently sloping lava-covered plateau which controls the upland topography has been trenched by deep canyons of the westward flowing streams, which are cut to depths of as much as 2000 ft. below the crests of the ridges. The district is about 18 miles from Nevada City but the automobile road which connects the two places is 31 miles long. The senior writer first visited the district in 1913 and published a short description of the lode deposits.1 The increasing importance of the district made further study desirable. A detailed topographic map was therefore made by W. B. Upton, Jr., of the U. S. Geological Survey, in the spring of 1924, and the senior writer spent parts of the field seasons of 1924 and 1925 in the district. For the second field season the Geological Survey was fortunate in securing the services of R. W. Gannett, who had already done geologic work in the district for several of the mining companies. Owing to the death of Mr. Gannett in October, 1925, just before the close of his field work, the work of preparation of the entire report fell to Mr. Ferguson. He takes this opportunity of acknowledging how deeply he is indebted to Mr. Gannett for his excellent work in the field, and his realization of how greatly the completion of the report on the district has suffered from lack of Mr. Gannett's assistance in the office. In October, 1.928, after the completion of the first draft of the manuscript, Mr. Ferguson made a short visit to the district.

Jan 1, 1929

By Reno H. Sales

EVERY mine manager, mine geologist, and every prospector in the field who appraises the future of mining properties does so on the basis of a theory of ore deposition whether he recognizes this fact or not. Wherever the ultimate value of a mine or prospect is dependent upon undeveloped ore, any estimate by an engineer or geologist necessarily involves a theory of origin of the deposit. In view of these facts the importance of a thorough understanding of the genesis of ore deposits cannot be overestimated. It well may be that the greatness of our country will depend upon finding reserves of natural resources as yet undiscovered. The genesis of ore deposits offers a fascinating field for study and investigation. This is attested by the large number of geologists who have written at length on the subject. For progress made toward a better understanding of ore genesis we owe much to Kemp, Lindgren, Ransome, Vogt, Emmons, Spurr, Graton, and a host of others. Within my own experience, I have attempted to apply in practice the various concepts and theories that have been advanced by these men.

Jan 5, 1954

No. 364.-Asbestos mine in Canada desires assistant mine superin¬tendent to supervise mining of ore and delivery of same to mill bins. To be successful, applicant should be good organizer and able to get production at right cost; one with experience on steam-shovel rock work preferred. Knowledge of French desirable. Salary $175-$200 per month; permanent position; chance for advancement. Company¬ owned houses available at nominal rental. No. 365.-Research metallographist. Man of commercial experience in alloy steels for position offering opportunity for constructive work over wide range of alloys, with large concern providing ample working facilities. In replying please give full details of training; experience, age and salary desired. No. 366.-Engineer to do surveying and making of mine maps cover¬ing inside development of mine as well as property outside of the-mines. Matter of salary depends on man's experience and efficiency. No: 367.-Engineer, preferably single man to be detailed mostly on mine surveying. Salary to start $130 per month and expenses while on the road.

Jan 2, 1919

By T. L. Joseph

THE invention of the Bessemer converter process in 1856 added great impetus to the manufacture of steel and is one of the outstanding contributions to process metallurgy. Although the process of refining pig iron by passing air through the molten metal bears the name of Henry Bessemer, it should be mentioned in passing that William Kelley of Eddysville, Ky., worked on the process as early as 1847. Kelley was granted a patent on the process in 1857, inasmuch as he was able to prove priority in discovery.1 After considerable litigation in 1865 the respective interests of Kelley and Bessemer were combined. On Sept. 10, 1856, Robert Mushet of England obtained his first patent on the application of manganese to cast steel. Mushet anticipated trouble in purifying iron by passing currents of air through it. His patent specified that steel made in this way often contained flaws and was red short or cold short. Mushet understood the refining of pig iron into steel well enough to realize the difficulties likely to be encountered from oxidation of the iron. Mushet was not only an inventor but he was also an investigator. He understood the principle of selective oxidation which takes place in the converter process, arid he realized therefore that the remedy for over-oxidation was attainable if a suitable metal could be found at a reasonable cost and in sufficient quantities. His first experiments were made in small crucibles holding a few ounces of metal. Later his work was conducted on a larger scale and with complete success. Manganese had been used in making steel a quarter of a century before the converter

Jan 5, 1927

By L. E. Wemple

Previous to 1915, zinc refining had not become a general practice among the zinc smelters in the United States. Such refining as had been carried on was confined chiefly to remelting very high-leaded zinc, such as third-draw metal from the retort furnaces, and slab dross, and hard spelter from galvanizing pots. In this remelting operation, the lead and iron were settled out and the refined spelter obtained graded fifth class, ie., Prime Western. Owing to the presence of lead in most zinc ores, the bulk of the spelter produced by direct smelting is of this Prime Western grade. Careful selection of ores of low lead content gave purer grades of spelter, z.e., Brass Special and Intermediate; and smelters which could secure ores carrying practically no lead produced high-grade spelter. Thus, in general, the grade of spelter produced by any smelter was predetermined by the purity of the ore it could obtain. The needs of the warring nations of Europe for enormous quantities of cartridge and other high-grade brass resulted in such a demand for the purer grades of spelter that the available supply of lead-free and low-lead ores could not produce the quantity required. Prime Western grades went begging, so to speak, while high grades sold at times from 5 to 15 c. per pound over the Prime Western market. The great demand, coupled with the wide market margin, which permitted the inherent costs and losses, resulted in the conversion of the lower grades into higher grades by processes of refining. These conditions also accentuated the development and size of the electrolytic plants, which were being worked out at the time this increased demand for pure grade of metal occurred. The electrolytic process, where available, produces a higher grade of spelter from impure ores than does the fire process; a large portion of those impurities in the ore, which by the distillation process would be carried into the spelter, are removed in the leaching of the ores and the purification of the solutions. The refining process, adopted at a number of smelters for the purpose of converting low-grade spelter into grades suitable for bras4 was that of redistillation.

Jan 1, 1918

By Chester Fulton

IN Polk County, Florida, the mining of raw phosphates began some 50 years ago with dredging operations on the Peace River, and in other near-by places by removal of shallow overburden with negroes and wheelbarrows, or with mules and scrapers, and the excavation and screen-ing of deposits found close to the surface. There were many individual operations of comparatively short life. Later steam shovels removed the overburden, and still later hydraulic methods were substituted for the steam shovel. Within the last 10 years large electrically operated drag-lines have almost entirely replaced hydraulic mining for overburden removal. The matrix is still mined by hydraulic giants and pumped to the washer or recovery plant. The many small operations have long since disappeared and the most desirable phosphate lands have gradually been acquired through purchase or merger by the seven companies that are operating in the field today. These companies are producing and selling about 2,000,000 long tons of phosphate per annum, or about two-thirds of what the industry likes to think is the normal output, with 1929 and 1930 in mind. To produce these 2,000,000 long tons of raw phosphate, they mine and treat about 1,000,000 tons of tailings from older and less efficient opera-tions, about 11,000,000 tons of matrix, and remove from above this matrix some 22,000,000 tons of overburden. The mining practice that has made possible the excavation and handling of 34 million tons of material to win but 2 million tons of merchantable product, selling for probably an average of only $4 per long ton when dried, should be of interest to the mining profession, though little has been written of it. The Florida Pebble Field, as it has come to be known, comprises an area (Fig. 1) within a radius of about 18 to 20 miles centering around Mulberry in Polk County, a small town 30 miles east of Tampa, Florida's largest port on the gulf coast.

Jan 1, 1936

By S. L. Hoyt

IN technological studies on steel considerable emphasis has been placed on the identification of the foreign inclusions, testimony of which is adequately given in the metallographic literature covering methods for their identification. The outstanding accomplishment in this field is the scheme devised by Campbell, Comstock and Wohrman for identi-fying various oxides, sulfides, silicates and other constituents by syste-matic etching tests and microscopic examination.1 The time involved in carrying out this procedure has led to attempts to secure quicker methods, or at least to shorten the time required to secure essential information. An example of this is the use of dark field illumination, but when this was tried out by the authors it was found that cavities and pits on the polished surface appeared bright on a dark field and could not be distinguished from small glassy inclusions. Still another means is the Leitz Ultropak, an instrument equipped with optical units for the illumination of the specimen by reflected light to secure an effect similar to dark field illumination. The structures are made visible in exceedingly sharp details by utilizing the inherent properties of the samples, such as refractive index, absorption coefficients and reflection powers. We have had no experience, with the Ultropak, but a recent paper by Benedicks and Löfquist3 describes methods for

Jan 1, 1934

By A. C. Watts

FOR several years, a mine in Colorado experienced considerable trouble from small fires caused by the blasting of coal. Although a well-known make of permissible powder was used, it was first thought that the powder ignited gas that might be present and that this, in turn, set fire to line brattices or to the coal. Experiments were, therefore, conducted with another make of powder, but the results convinced the superintendent of the mine, Robt. Williams, Jr., that the fires were not caused by the powder but by the high-voltage electric current used for detonating the shots. The mine "makes" gas very freely, giving off from three-fourths to a million cubic feet of methane per 24 hours. The coal is a good grade bituminous of a very free burning quality. Electric shot-firing from the outside after all men and animals were outside had been practiced for a number of years. The shooting circuit was connected with the main power circuit at the mouth of each entry. Shooting circuit switches were mounted in boxes, which were kept locked with the handle of the switch, in open position, showing through the bottom of the box. The door of the box could not be shut and locked when the shooting switch was closed. At the entrance to each room, or working place, a small switch, called the miner's switch, was placed on the shooting line. It was the duty of the miner, when entering his place at the beginning of the shift, to see that this switch was open and that it was kept open until he left the place at the end of the shift to go out of the mine. Grounded return was used for main power lines. The current was 500 volts, direct current, with 100 to 300 amp. The nearest working face was 9600 ft. from the shot-firers' switch outside the mine and the most remote working face was 2 ½ miles. The various working faces were scattered over a wide area between these two points.

Jan 9, 1925

By John Skelton, E. J. Harvey

Seepage runs (stream flow measurements in a short time at many points in a basin,) and stream flow records are used to locate losing areas in stream basins in the Missouri Ozarks. The terrane consists of dolomitic limestone and sandstone of Ordovician and Cambrian age. Side-looking radar imagery emphasizes variations in topography and reveals two types of drainage basin topography, rough and smooth (deeply dissected and slightly dissected basins). In the deeply dissected basins (rough ones), main streams and tributaries generally gain. In the slightly dissected basins (smooth ones), the streams lose a part or all of their flow. Logan Creek, a tributary of Black River in the southeastern Ozarks, loses much of its storm runoff and all of its dry weather flow. East and West Forks of the Black River, north of Logan Creek, gain water through most of their main stems. On radar imagery Logan Creek basin has a light uniform tone and smooth texture in contrast to the darker tone and rough texture of the East and West Forks. The contrast is due to the difference in degree of dissection. Therefore, radar imagery may be useful in suggesting gaining or losing streams (or reaches of streams).

Jan 1, 1973

L. C. UREn,* BerkelEy, Cal. (written discussion).—I heartily concur with Rlr. .Fobs concerning the need for advanced courses on various phases of Petroleum Engineering. I think that his criticism is probably true of most of the engineering schools that are specializing at all in Petroleum Engineering, that is, that most of their so-called graduate courses are not of graduate caliber but are merely more specialized aspects of undergraduate subjects. It would undoubtedly be to the advantage of the petroleum profession if more advanced work could be offered in a few of the leading engineering institutions so that there would be something substantial to offer graduate students wishing to return after a period of undergraduate work, for additional training. There is no doubt but that a better trained engineer, more useful to the oil industry, could be secured from schools offering such advanced training. The problem of adpting our instruction to fit the needs of engineers trained along other lines who wish, after completion of their undergraduate work, to enter thc petroleum engineering field, is a more difficult one. It has been my experience that such men are usually sadly deficient along certain lines and that they are really not prepared for the more advanced work in Petroleum Production Engineering until they have gone back over the work which they have missed in their undergraduate training. I note that Mr. Fohs suggests that other eastern and western colleges not now stressing Petrolelim Engineering, should be encouraged to take up advanced work of this character. With this, however, I cannot agree unless the institutions arc also prepared to offer a full sequence of undergraduate work on which the more advanced courses may be superimposed. Whether or not there is a need for additional engi-ncering colleges entering the petroleum engineering field is an open qucstion. I believe that we arc turning out enough petroleum engineers at the present time and that none of the six institutions now specializing in this field arc overcrowded. Morc-ovcr, they are fairly well distributed over the country, though there may be room for an additional school in the field in the eastcrn section of the United States. F. W. Padgett, Norman, Okla. (written tliscussion).—Assuming that the stnclcnt has the proper fundamentals, that is, general science and a knowledge of the technology of the industry, then the problem is: What courses should be offered from the graduate standpoint? (a) Course Work.—His knowledge of the technology of the industry can be extended advantagcously by means of one and two-hour courses, which consist in a more detailed survey of the various branches of the industry. (b) Lilerdure.—This work may, or may not, be connected directly with his research problem. The student should become familiar with methods of locating articles in the 1iterature; should also become familiar with all the important original

Jan 1, 1928

By J. L. Huitt, B. B. McGlothlin, J. J. Day

Laboratory tests were made with pure minerals and actual reservoir rock samples to study the effects of hydrothermal (steam m hot water) treatments on reservoir rock properties. These tests showed that hydro-thermal treatment of many reservoir rocks can result in significant rock softening. The softening was attributed primarily to the partial destruction of dolomite and kaolinite and the synthesis of montmorillonite in the presence of excess silica. In many cases, the softening was great enough to cause considerable healing of propped fractures; therefore, a serious reduction in welt productivity could result. In other tests it was found that the addition of ammonia to a hydrothermal treating fluid in a concentration as low as 0.013 Ib/lb of water not only could prevent rock softening but could cause rock hardening. The results of X-ray diflraction analyses of rock samples showed that when ammonia was added to the treating fluid, ammonium-mica and analcite were formed instead of montmorillonite. No significant permeability damage was observed in the sandstones that were subjected to the ammonia-hydro-thermal environment; in some sandstones, permeabifity improvements resulted. INTRODUCTION As the use of steam or hot water becomes more prevalent in well stimulation methods. the need for information on the effects of such treatments on reservoir rock properties becomes increasingly apparent. Several works have been published on high-temperature changes in rock properties,',' but these are more applicable to in situ combustion operations than to steam or hot water injection processes. The mineralogical literature contains many publications which report on the changes occurring with various pure minerals in hydrothermal systems. A review of this literature denotes the ease with which entirely new, crystalline mineral phases can be synthesized from other minerals in hydrothermal environments at temperatures, pressures and residence times typical of those encountered in oilfield thermal recovery or stimulation processes. Discussions of many of these experiments are given by Deer et al. Grim,' Roy et al., Zen\ and Hawkins.' One of the most significant of these pure mineral studies is the hydrothermal synthesis work of Levinson and Vian" in which montmorillonite was synthesized from naturally occurring minerals; i.e., kaolinite, quartz and carbonate minerals (particularly dolomite). These reactions occurred at 575F in only 2 days and at 300F in 5 days. These results may be applicable to petroleum reservoir rocks since the minerals studied were those which are commonly found in sandstones. Furthermore, the environmental conditions imposed in the studies were very similar to those involved in thermal stimulation of petroleum reservoirs, e.g., steam or hot water injection. Other studies have suggested that weak rocks could be hardened by "electrochemical induration", a process in which an electric current is applied to a clay-containing rock body. These tests can be regarded as hydrothermal treatments since they were conducted in some instances with aqueous solutions and since clay temperatures during the electrical treatment reached a maximum of about 100C. Although a number of studies of the reaction of pure minerals have been reported, very little has been published on the reactions of petroleum rock-hydrothermal systems. No work has been reported on preventing the more detrimental rock changes in rock softening which might occur during the injection of steam or hot water into reservoirs. The studies described in this paper were conducted to provide such information. EXPERIMENTAL APPROACH The laboratory tests included studies of the effect of hydrothermal treatment on core samples from several different reservoirs. The hydrothermal treatments (simulated steam treatments) were conducted with distilled water at 575F, for the most part, for periods of 2 to 6 days. This temperature level was selected because it represented that temperature which would probably prevail in several cases under consideration for steam injection projects. The core samples, as well as the pure mineral samples, were contained in high-pressure stainless steel, autoclave-type pressure vessels. The effects of the hydrothermal treatments were evaluated by measuring the penetrometer hardness, formation rock embedment strength and permeabilities of the core samples before and after the treatments (Fig. 1)'" In addition, the mineralogical changes in the specimens were studied by X-ray diffraction. Concomitant with the core sample studies, the mineralogical changes were studied in greater detail by conducting hydrothermal synthesis experiments with pure minerals at similar temperature levels and residence times. For the most part, samples of finely-crushed pure dolomite.

CALAMINE is one of the semiminerals that have great similarity to the metals. It is a very heavy mineral earth of a yellowish color. It is found in Germany near the lead mines and in Italy in a mountain between Milan and Como. It is also found, as I have heard, in other places, as at Fosini in the territory of Siena. I believe that it is almost certain that some exists there because there are many other kinds of minerals there- about, although none is mined there in these times. But this does not mean that it could not be mined or that there is not some there that is real. Someone says that he med to melt what he could find with copper [36v]

Jan 1, 1942

By Sidney Powers

CONTENTS PAGE Distribution of fields 4 History of development 6 Origin of oil 7 Structure,, accumulation and migration 8 Reservoir rocks 9 Methods of drilling and exploration to Oil-field statistics 12 Description by regions: United States: Appalachian region 12 East-central states 17 Kansas 18 Oklahoma 19 Texas 24 Arkansas 32 Louisiana 33 Mississippi -.. 34 Rocky Mountain region 34 California : 37 Canada 41 Mexico 43 Cuba 46 Bibliography 46 THE purpose of this brief account of the occurrence of petroleum in North America is to make available to those who have a knowledge of geology, but who are not engaged in the petroleum industry, a few salient facts about the location of oil and gas fields, their productivity, the important structural types of accumulation and the age of the rocks containing petroleum. A few useful data and statistics are furnished, yet not complete statistics that are available elsewhere. Geology has been treated in simple terms because the reader is presumed to have little interest in the names of formations and of oil sands. Mineral deposits are more or less analogous. Whether oil or metals, minerals are found in rocks, largely in sedimentary rocks which carry water or have at one time carried it. A genetic or accumula-

Jan 1, 1931

By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954