Search Documents

By Peter F. Weiss

INTRODUCTION Austro-American Magnesite Co. of Radenthein, Carinthia, Austria, is a wholly owned subsidiary of General Refractories Company, Bala Cynwyd, USA, and has been incorporated since 1908. The raw material basis is the magnesite mine on Millstatt Alp, located in the mountains near Radenthein at an altitude of 1500 m above sea level. The mined crude magnesite is crushed in a surface crushing plant to minus 35 mm and consequently hauled to the processing plant in the valley by means of a cable conveyor of 7.5 km length. The annual production of 350,000 mt is accomplished with 20 supervisors and 122 workers (of those 60 are in the mine). The labor requirement for block caving is 0.2 man hr/mt, corresponding to an output of 40 mt/man/ shift. GEOLOGY The rock in this area mainly consists of crystalline type schist. There are mostly coarse crystalline garnet mica schists with varying mineral concentrations, and to a lesser degree, some deposits of amphibolite and marble. This petrographically rather homogeneous rock is divided into numerous different tectonic units (covers and scales). The magnesite deposit itself is a foreign body that also has been tectonically inserted. The ore body has a length of 600 m, is 450 m deep, and has a thickness of 60 m on average, varying substantially however, The contact with the accessory rock is very precise. The deposit 1 = ore body, 2 = previous open pit, 3 = caved in area, 4 = block under excavation, 5 = land slide consists of coarse crystalline magnesite in excess of 90 per cent. The few impurities consist of dolomite and talc. The lower part of the deposit is inclined parallel with the schists at approx. 40 degrees. In profile it can be seen, however, that the upper part of the deposit has been tilted over. This is a result of a post-glacial land slide reaching from the bottom of the valley at 1400 m above sea level to the peak of the mountain at 2100 m above sea level. Due to this land slide, with horizontal movements of up to 100 meters, as well as older tectonic events, the rock was crushed to a vast extent. Through mining, the land slide was reactivated; about 40 million cubic meters of rock slowly flow downhill almost like a plasticized mass. Near the surface, the rock is completely crushed and resembles a glacier rupture zone. This renders the originally impermeable rock completely water permeable so that practically all of the annual quantity of 1000 to 1100 mm of precipitation permeates the rock and flows down into the mine. The carbonate rock turns into the preferred aquifer. From 1700 to 2600 cubic meters of water have to be pumped from the mine daily. On one hand, additional problems are caused by the water in the mine, on the other hand we have learned to make use of the down- hill pressure forces to improve the crushing process during block caving. The boundary of the downhill shearing zone moves downward as mining goes deeper.

Jan 1, 1981

W. ROWLAND Cox,* New York, N. Y. (written discussion?).-The process described by Mr. Malcolmson undoubtedly represents a great stride toward conservation of our natural resources. Without discussing the subject from an economic standpoint, I wish further to emphasize the fundamental principles of the Smith process in order that its economic value may be fully appreciated. The process is essentially a means of producing an ideal fuel, as regards its combustion qualities, by the removal of the so-called volatile matter from the coal, in the form of byproducts, which have value for other purposes far in excess of their fuel value. In other words, coals which contain. large amounts of gas, tar, and ammonia, and are not suitable for domestic or industrial fuel, or for treatment in byproduct coke ovens or gas retorts; because they possess poor coking qualities, can he prepared for commercial use by the. Smith process with a very high degree of efficiency. Much work has been done along this line, both in this country and in Europe, in developing a means of preparing coal, as the economic advantages have long been recognized. To the best of my knowledge, the Smith process is the only one that has proved its commercial adaptability. Distillation of coal at 900° to 1000° F. (480° to 540° C.) yields a large amount of tar and oils. The residue of the distillation, however, is a very friable semi-coke, wholly unsuitable for use as a fuel, unless it can be charged directly into a byproduct gas producer. The problem which confronted the inventor was then to convert this carbon residue into a commercial product, and it is in this step that the Smith process has overcome the obstacles which prevented a number of other methods from becoming commercially practicable.

Jan 10, 1918

By Milton E. Wadsworth, J. Brent Hiskey

Galvanic interaction between particulate chalcopyrite (CuFeS2) and copper results in the rapid conversion of chalcopyrite to chalcocite. The effects of temperature, surface area, concentration of sulfuric acid and agitation were systematically evaluated. The kinetics were found to be controlled by a steady-state current flow controlled by the effective anodic and cathodic surface areas involved in the galvanic couple. The experimental activation energy was 11.5 and stoichiometric data and reaction products have been characterized. The overall kinetic system has been evaluated based upon an electrochemical model.

Jan 1, 1974

By Lawrence Addicks

THrough the courtesy of Dr. James Douglas I am permitted to give a summary of some of the results obtained in leaching slimes tailings in a series of experiments conducted under my direction at Douglas, Ariz., during the past year. While the test run for which the data are given deals with a particular case, much of the work is general in its application and may therefore be of interest. This work was done upon the ores of the Burro Mountain Copper CO. A description of the geology of the district will be found in the paper by R. E. Somers published in this volume, p. 604. The mineral is pyrite and chalcocite very finely disseminated throughout the gangue and a characteristic of all the ores is the large amount of alumina present. A representative analysis of the particular ore under consideration would be about as follows: Cu, per cent..................... 2.35 S, per cent...................... 3.0 Ag, ounces per ton.............. 0.05 CaO, per cent.................. 0.5 Au............................ None K2O, per cent.................... 4.0 Fe, per cent..................... 1.50 SiO², per cent.................... 70.0 Alz²O³, per cent....................13.OO The leaching of the ore direct was early dismissed from consideration for the following reasons: 1. The ore would have to be quite finely crushed to liberate the mineral for leaching; concentrating after crushing would cost but a few cents a ton; and a higher total reeovery would result from leaching tailings rather than ore. 2. Rough concentration would yield a suitable material for roasting to make sulphur dioxide or sulphuric acid in connection with the leaching scheme. 3. Such a program put the question of cost vs. recovery on a basis where flotation and discarding of tailings were directly comparable. Concentrating experiments already available indicated that the tail-

Jan 1, 1916

By Edmund C. Pechin

I REGRET that I am unable to present this subject in definite form and detail. All I shall attempt at this meeting is to lay before you some curious facts, the bearings and explanations of which must be reserved for future consideration. I hope before the next meeting to have carried experiments far enough to furnish a more important contribution to the science of iron metallurgy. The Wickersham process consists in the introduction into the molten metal, as it runs from the furnace, of air from the hot blast. Mr. Samuel Wickersham is the originator of the plan, as applied in practice, although Mr. Martien had the idea a long time ago, and, I believe, .went to England about it. But at that time Mr. Bessemer was coming before the public with his invention, which engrossed the attention of iron-masters, and Mr. Martien accomplished nothing. The principal difficulty in our experiments at Dunbar was to get a practicable runner or trough, through which the molten metal should pass, and in which it should be exposed to the action of the blast. The runner we used was ten feet long, and perforated on the sides to permit the entrance of the air-currents. When we used a cast-iron and fire-clay runner, the heat was so great that before we were more than half done with a run, the lower part of the runner was melted, and we had a magnificent Fourth of July display of fireworks until the blast was shut off. We had to abandon fire clay. The runner with which we have had the best success ,is made of wrought-iron tubes, 2 1/2 inches in diameter, attached to a wrought-iron frame, and lined with a mixture of crushed conglomerate (quartz) and a little fire clay to give it cohesion. The wrought-iron shell curves inward over the upper edges, so as to catch and throw back into the current the flying sparks and particles of metal thrown out by ebullition. With this we have been able to run 12 to 14 tons at a heat with great ease. Mr. Wickersham has since prepared this material (pounded quartz) into a shaped brick or tile, with the necessary perforations for the passage of the air, which promises to answer every requirement for steady working. As regards the improvement in the quality of the iron, there seems to be no question. A large number of practical tests were made in

Jan 1, 1873

By J. M. Steininger

The mechanism of flotation of sphalerite with sulthydryl compounds of different acidities has been interpreted in terms of chemisorption of unionized collector molecules on hydroxylated zinc surface sites. At a constant collector concentration of 1.5 x 10 -4 M, the upper pH limit of flotation has been found to be directly and closely related to the negative logarithm of the collector acidity constant, pKa The experimental results indicate that flotation is prevented when about 95% of the collector is ionized. At low pH, collector adsorption decreases because of the reduction in number of hydroxylated zinc surface sites. These two effects explain why sphalerite does not float with the more acidic sulfhydryl compounds. Typical anionic collectors for sulfide minerals are short chain xanthates or dithiophosphates which are nearly completely ionized in the generally alka- line flotation circuits.1,2 Flotation mechanisms have therefore been usually interpreted in terms of ionic collector adsorption and competition with ionic depressants of the same sign as the collector. A few attempts have been made, however, to consider adsorption of neutral collector molecules. Contact angle measurements obtained by Wark and cox3 have been interpreted by Cook and Nixon4 as representing adsorption of the free acid molecules on sulfide minerals such as pyrite, galena, chalcopyrite, and sphalerite. Cook and Nixon tried to show that the free acid concentration of the collector was substantially constant along the curves relating collector addition and minimum pH for bubble adherence. However, in a review of the subject,5 Sutherland presented new data on the flotation of pyrite with mercaptobenzothiazole which did not support the hypothesis of constant concentration of either collector ions or collector free molecules. He further showed that, with the assumption of constant occupation of surface sites, both theories lead to relations between pH and collector addition having similar mathematical expressions. In fact, with the more likely assumption of variable occupation of surface sites which results in more complex relationships, it appears impossible to

Jan 1, 1968

I HIT the ceiling when I opened my November MINING ENGINEERING and after waiting a week to cool off I' still find it necessary to express my resentment of the gross libel embodied in the editorial introduction to Norman Stines' legitimate criticism of my paper on "Russia's Mineral Potential" (p. 949). The underlying thesis of my article, and a point that I tried to make even more clearly in my oral presentation at the St. Louis meeting last February, is that we should not over estimate the present and near-future mineral production of the USSR. The words that I resent in your boxed introduction are: "Opinions range from those presented by Paul Tyler ... to those of Norman C. Stines . . ." This is not merely an understatement that can be defended by admitting that the range goes much farther to the left, beyond me. It represents the appraisal that 90 pct of your members will carry away, namely that I am not only an incompetent observer-which may be true-but always that my bias is to applaud the efficiency of the beasts in the Kremlin-which is not true. Notwithstanding my efforts to clarify the record I now find myself branded as being at the opposite pole from 'Mr. Stines among the red-eyed worshipers of Communism or at least among the timid souls that shake in their boots in the belief that the Soviet system has created an invincible as well as an evil menace to the decent peoples of the world. My ideas are somewhere in the middle ground between Mr. Stines' complaisance or contempt and the exaggerated fears of several other observers whose views have received wide acceptance. PAUL M. TYLER MINERAL TECHNOLOGIST & ECONOMIST 5005 EDGEMOOR LANE, BETHESDA, MD. The introductory paragraph to Mr. Stines' criticism of Mr. Tyler's article (Russia's Mineral Potential, June issue MINING ENGINEERING, page 494) is erroneous as pointed out in author Tyler's letter above. In his article he objectively presented an estimate of the mineral position of the Soviet based on the statistics available to him which sources are credited in the first paragraph of his article. We happen to know that, Mr. Tyler was reluctant to prepare the article for the Mineral Economics Division sessions at the 1951 Annual Meeting and did so only because of his loyalty to AIME. It was thought that this article would be a basis for discussion of this important subject at the Annual Meeting. We apologize to Mr. Tyler for any embarrassment our introduction, may have caused him. Editor

Jan 1, 1952

By F. I. Grace, L. E. Murr

The mechanical responses and residual defect structures in 70/30 brass and type 304 stainless steel following explosive shock loading and cold reduction by rolling have been studied. A distinct relationship was observed to exist between the residual mechanical properties and micro structures observed by transmission electron microscopy. Shock-loaded brass deformed primarily by the formation of coplanar arrays of dislocations and stacking faults at lower pressures, and twin-faults (deformation twins and €-martensite bundles) at higher pressures (> 200 kbar). The micro -structures of cold-rolled brass were characterized by dense dislocation fields elongated in the rolling direction. Stainless steel was observed to deform by the formation of dense arrays of stacking faults at lower shock pressures and twin-faults at high shock pressures (>200 kbar). Lightly cold-rolled stainless steel deformed similar to low Pressure shock-loaded stainless steel, but transformed to a' martensite in heavily cold-rolled stainless steel. Discontinuous yielding was observed for the heavily cold-rolled stainless steel, and stress reluxution in the weyield region for cold-rolled and shock -loaded stainless steel was interpreted as an indication of the ability of twin-faults and stacking faults to act as effective barriers to dislocation motion. A simple model for the formation of the planar defects and a' martetnsite is presented based on the propagating of Shochley partial and half-partial dislocations. A considerable effort has been expended over the past decade in an attempt to elucidate the response of metallic-crystalline solids to the passage of a high velocity shock wave (e.g., smith,' Dieter,2 and zukas3). While it has been possible to obtain relevant information pertaining to the residual defect structures and mechanical properties, there have been few rigorous attempts to draw a direct comparison between these structures and properties. In addition, numerous investigators have recently observed the occurrence of deformation twinning in shock deformed fcc metals (e.g., Nolder and Thomas,4 and Johari and Thomas5), but little attempt has been made to elucidate the mechanisms of formation of these defects. Comparative data for metals deformed by shock-loading and the same metals deformed by more conventional modes of deformation such as cold-reduction by rolling is also generally lacking. The present investigation therefore has the following objectives: 1) to examine the mechanical properties of some explosively shock loaded and cold-rolled fcc metals of low stacking-fault energy as a function of their residual substructures; 2) to present a simple model for the formation twin-faults and related defect structures in the low stack-ing-fault energy materials of interest (70/30 brass, ySFg= 14 ergs per sq cm; and 304 stainless steel, ySF = 21 ergs per sq cm); 3) to make some deductions with regard to the residual characteristics of dislocation and planar defect substructures in cold rolled and shock loaded 70/30 brass and type 304 stainless steel. In particular, it was desirable to characterize the residual hardening effects of particular deformation substructures. I) EXPERIMENTAL PROCEDURE Sheet samples of 70/30 brass (0.005 and 0.15 in. thick; annealed at 659°C for 2 hr) and type 304 stainless steel (0.007 in. thick; annealed 0.25 hr at 1060°C) of nominal compositions shown in Table I were cold-rolled in one direction only to produce reductions in thickness of 15, 30, 45, 60, and 75 pct in the brass; and 5, 15, 25, 35, and 45 pct in the stainless steel. Identical sheet samples in the annealed (unrolled) state were subjected to plane compressive shock waves to various peak pressures ranging from 0 to 400 kbar in the brass and 0 to 425 kbar in the stainless steel; and with a constant peak pressure duration of approximately 2 microseconds. A detailed description of the shock loading technique has been given previously.6 Tensile specimens 1.0 in. in length and 0.125 in. in width were cut from the cold-rolled sheets (tensile axis parallel to the rolling direction), and the shock-loaded sheet specimens. Stress (load)-strain (elongation) measurements on the tensile specimens were made on a Tinius-Olsen load-compensating tensile tester using a strain rate of 2.7 x 10-3 sec-1. Tensile tests were repeated at least twice, giving essentially the same results. Stress relaxation measurements in the preyield region were also made using an initial strain rate of 5.4 x 10-4 sec-1. In addition to tensile and stress relaxation measurements, Vickers microhardness measurements were made on all samples. A total of 100 microhard-ness readings were obtained for each specimen following a light electropolish to ensure uniform surface conditions for all tests. The hardness averages ob-

Jan 1, 1970

Jan 1, 1928

Jan 1, 1951

By S. Ramachandran, R. A. Walsh

Many investigations have shown that the manganese enhances the deoxidation power of silicon. Here it is suggested that this phenomenon could be explained in terms of the formation of impure silica. Data of Hilty and Crafts on the Fe-Mn-Si-O System has been evaluated on the basis of the reaction S_i + 20 = (SiO2) where (SiO2) denotes silica of variable activity. The activity of silica in this system is a function of aMn/aSi and the temperature, and can be described by the equation 12700 l°gaSiOz = -6.85+ - - 0.5 log aMn /asi PRACTICAL melting experience has shown that it is helpful to maintain a certain range of Mn/Si ratio in deoxidizing quality alloy steels. Herty,1 as early as 1932, reported a strong association between manganese and silicon as did schenck2 and Korber and Oelsen3 in later work. More recently, Hilty and crafts4 have studied the solubility of oxygen in the Fe-Si-O system, both with and without manganese. Their study confirmed the marked ability of manganese to increase the deoxidizing power of silicon. This phenomenon has remained unexplained in the liter,ature5 since it has been shown that manganese has virtually no influence on the activity coefficients of silicon or oxygen.= In this paper, an explanation for the role of manganese is suggested and equations are devised for quantitatively describing this influence. DISCUSSION Hilty and crafts4 equilibrated their melts under an argon atmosphere and the system established equilibrium with a self-generated slag which was not always the oxide of lowest free energy. Drawing on the early work of Korber and Oelsen,3 it was reasoned that the formation of complex Fe-Mn-silicates

Jan 1, 1963

YEAR OF ELECTION 1913. FRANK DAWSON ADAMS, Montreal, Canada. 1933. KARL EIKERS New York, N. Y. 1922. FEDERICO GIOLITTI Torino, Italy. 1906. SIR ROBERT A. HADFIELD London, England. 1921. FRANK WILLIAM HARBORD London, England. 1917. HERBERT HOOVER Washington, D. C. 1941. DANIEL COWAN JACKLING San Francisco, Calif. 1939. HENRY KRUMB New York, N. Y. 1921. C. McDERMID London, England. 1913. EZEQUIEL ORDONEZ Mexico City, Mexico. 1935. ROBERT PEELE New York, N. Y. 1938. A.M. PORTEVIN Paris France 1937. JOHN V.W. REYNDERS, New York, N. Y. 1937. GEORGE S. RICE Washington, D. C. 1911. ROBERT H. RICHARDS Cambridge, Mass. 1934. T.A. RICKARD Victoria, B.C., Canada

Jan 1, 1941

By Worthen Bradley

A BETTER understanding of what is happening in the domestic quicksilver industry, and what is likely to happen, can be had after reviewing some of the highlights of the past four years. Hitting the high spots in chronological order, they are: February 1939-Army and Navy Munitions Board starts investigation on civilian and war needs of certain "strategic materials," including quicksilver, with a view to recommending stock piles. Every known producer is canvassed by the end of the year.

Jan 1, 1942

By L. Sturkey

Quantitative X-ray diffraction studies of the precipitation of thorium in a Mg + 3.3 Th + 0.51 Zr alloy (HK31A) in both the as-cast and cold-worked states show that the precipitation may be described by f = 1 - e(t/T)1/2 over most of the aging period. The effects of cold work and temperature changes are determined. The precipitation of tile equilibrium Mg-Th compotund is Preceded by the formation of a transition phase of higher thorium content, with the cowposition Mg2Th and with a Laves-phase structure. Thorium-containing alloys of magnesium have assumed considerable commercial importance, especially for applications requiring exposures to temperatures greater than 500°F for appreciable lengths of time. The principal commercial wrought alloys in this system are HK31A, containing nominally 3 pet by weight thorium and about 0.7 pet by weight zirconium: and HM21A. containing 2 pet by weight thorium and 1 pet by weight manganese. These two alloys retain a high level of properties even after exposures of 100 hr at 600°F, while the more common alloys containing aluminum and zinc are badly overaged by these conditions. Therefore, in order to obtain some insight into the mechanism by which thorium produces high temperature stability in these wrought alloys, it seems desirable to investi- gate the effect of temperature and mechanical working on the precipitation processes involving thorium. Since the scattering power of a thorium atom for CuKa X-ray radiation is about ten times that for a magnesium atom, the magnesium alloys containing about 3 pet by weight thorium are ideal for quantitative measurements by X-ray diffraction of the amount of Mg-Th compound present at any time. Such quantitative measurements should be of theoretical importance in the study of the effects of time, temperature, and deformation on precipitation and precipitation hardening. Of the two commercial alloys, HM21A and HK31A, the latter is certainly the most suitable for study: In the Mg-Th-Zr2 system, only Mg-Th compounds need be considered, since no ternary compounds or binary Th-Zr3 and Mg-Zr4 compounds exist. The Zr is added to this alloy as a grain refining agent and probably plays a secondary role in precipitation. On the other hand. thorium and manganese form many

Jan 1, 1961

By Mowry Bates

The following example of the practical application of engineering geology is of interest in that it demonstrates the advantage of keeping accurate records of all wells, whether drilled by onn's self or by others, together with the advantage gained by gathering such data during the process of development. The fault described was found in the autumn of 1915, during the hurried development caused by the discovery of the famous Gusher Bend pool in Red River Parish, Louisiana. The writer was at the time employed by one of the operating companies as geologist, and the example is a portion of the routine work. Location The oil fields of northern Louisiana and east Texas are located in Caddo, Bossier, De Soto and Red River Parishes, Louisiana, and Marion County, Texas. A very narrow strip of the eastern portion of the latter is productive. The producing oil pools are known as the Caddo Field, in the northern part, and the De Soto-Red River Field, in the southern. The two fields are 60 miles apart. There are several gas fields between them, but no important supply of oil has been found, though there are several producing wells in the Anona chalk, locally called the Chalk Rock, in the Elm Grove gas field in Township 16 North, Range 11 West (see Plate 1). General Geologic and Structural Features The general geology of northern Louisiana has been excellently described by A. C Veatch in Professional Paper No. 46, U. S. Geological Survey; by G. D. Harris, Bulletin No. 429, U. 8. Geological Survey; and later by George C. Matson and Oliver B. Hopkins in Bulletins No. 619 and 661C, U. S. Geological Survey.

Jan 1, 1920

By Gregory L. Gullord

In September, 1975, production was begun at the new milling facility of ASARCO Incorporated, the Young Mill. The mill is located adjacent to the Young Mine 35 km (22 miles) east of Knoxville, Tennessee. The Young Mill replaced the obsolete Mascot Mill which had been operating since 1913. The basic flow sheet of Mascot was retained for the construction of the Young Mill, with a 20% increase in capacity included in the design. The Young Mill is capable of processing 7710 - t/d (8500 stpd) of crude ore from three underground mines (Young, Immel and Coy) yielding 300 - t/d (330 stpd) of 63% zinc concentrate. The Young Mill is unique in that 92.5% of the ore milled is recovered as saleable products, including zinc concentrate, construction aggregate, sand and agricultural limestone. Processing at the Young Mill is divided into five basic stages: two-stage crushing, heavy media separation, grinding-flotation, concentrate filtering and drying, and limestone by-products recovery. The ore bodies are located in the Knox formation, which consists of primary dolomite, secondary dolomite and limestone with silicas in the form of chert and jasperoid. The zinc mineralization occurs as an exceptionally pure sphalerite. The ore contains an occasional abundance of pyrite and traces of fluorite and barite. TWO STAGE CRUSHING Ore enters the crushing section from two points. The Young Mine ore is hoisted into a 816 ton (900 st) bin which feeds a 1.52m (60 in) conveyor via a 1.52 m (60 in) vibrating feeder. The Immel ore is trucked 10 km (6 miles) by an independent contractor and weighed on automatic recording truck scales at the entrance to the property.

Jan 1, 1977

United Engineering Trustees, Inc. ARTHUR S. DWIGHT GEORGE D BARRON J V. N DORR Engineering Societies Library Board ROBERT PEELE PHILIP W. HENRY GEORGE C STONE JOSEPH E. POGUE The Engineering Foundation H C BELLINGER GALEN H CLEVENGER J V N DORR

Jan 1, 1923

By M. M. Mebta, G. W. Dean, W. H. Somerton

With the advent of underground heating operations, interest has developed in the alteration of rock properties by high-temperature treatment. In the present work a number of sandstones were heated to temperatures in the range of 400°C to 800°C under both atmospheric and simulated reservoir pressures. Pertneabilities increased by at least 50 per cent and sonic velocities and breaking strerlgths decreased by an equivalent amount. Differential thermal expansion and other reactions of constituent min-era1 grains are the causes of these alterations. INTRODUCTION In the underground combustion of petroleum reservoirs, temperatures of the order of 600C are reported to have been reached in the combustion zone.' At this temperature rocks are subject to extensive thermal alteration. Temperatures of this magnitude and higher may also occur in subsurface formations when subjected to bottom-hole heating, thermal drilling operations, and underground nuclear explosions. Temperatures of this magnitude might also be generated by conventional rock drilling methods at points of bit-tooth contact. In earlier work, the permanent deformation of rocks resulting from heating was reported. Major structural damage of rocks occurs due to differential thermal expansion of mineral constituents. A number of mineral alterations including crystal inversions, loss of water of crystallization and dissociation, may also contribute to changes in physical structure and properties of rock. In the present work, samples of three typical sandstones were heated to several temperatures up to a maximum of 800C and then allowed to cool to room temperature. Heating was done under both atmospheric pressure and simulated reservoir pressure conditions. Physical properties of the samples were measured before and after heating and comparisons made. Measured properties included permeability, sonic velocity, breaking strength and fracture index. Changes in physical properties were compared to changes in mineralogical characteristics as determined by thin-section. X-ray diffraction and chemical tests. EQUIPMENT AND PROCEDURE Two outcrop sandstones (Bandera and Berea) and one sub-surface sandstone (St. Peter) were selected for the tests. These samples have a wide ranee in composition and physical properties as shown in Table 1. The first series of tests was made on 2-in. diameter by 5-in. long test specimens. Test specimens used in all later work were 3/4-in. diameter by 1 1/8-in. long, this being the specimen size required for heating at simulated reservoir pressures. After careful washing, the cores were oven dried at 100 ± 5C for a minimum of 24 hours before the tests were run. Test specimens were heated in an electric furnace at a constant rate of temperature increase of 3C per minute. When maximum temperature of the run was reached, the sample was allowed to soak for one hour. The furnace was then cooled to room temperature at the same rate of 3C per minute. The entire heating operation was designed for reproducibility without subjecting the test specimens to excessive thermal shock. For samples heated under simulated reservoir pressures, a pressure cell designed by Dean was used (Fig. 1).3 The core sample was inserted into a thin-walled (0.006 to 0.01-in.) copper cup which was then mounted in a high-pressure cell. Provisions were made for the application of internal pore pressure as well as confining pressure. Tests showed that the thin-walled copper cup closed tightly around the core and satisfactorily transmitted confining pressure to the core. The core was heated by placing the entire cell into the electric furnace. The heating program was the same as that used in the atmospheric pressure runs: tempera-ture rise of 3C per minute to maximum temperature of the test, soaking at maximum temperature for one hour, and cooling at a rate of approximately 3C per minute. The cell was designed to withstand 5,000 psi at 1,000C. However, since it was considered likely that repeated heating and cooling would in time weaken the steel, 2,000 psi at 850C was set as a working limit. In the present series of tests, the pore pressure was held constant at 750 psi and the confining pressure at 1.500 psi. The pressure source was a high-pressure nitrogen tank. The two pressures were controlled manually but are accurate well within ± 50 psi.

Jan 1, 1966

By G. B. Thomas

Several methods of analyzing pressure build-up data in wells have been presented by various authors. This paper reviews the theory and method of D. R. Horner and presents example calculations performed on data obtained by testing several different types of wells. These calculations include, (1) graphical estimation of final static pressure, (2) determination of the productive capacity of the pay away from the well bore and. (3) the degree to which the formation adjacent to the well bore has been damaged by completion or other causes. The methods of testing and precautions which should be taken to assure the best data possible are discussed. Limitations and reliability of calculated results are also treated. INTRODUCTION Pressure testing of wells is generally limited to the determination of producing and static mean formation pressures. The so-called "static" pressure determination.. along with PVT, electric log and production data, enable the reservoir engineer to determine, within reasonable limits, the drive mechanism of the reservoir and in some cases. the amount of edge water encroachment. Producing pressure tests enable calculation of productivity indices and allow the engineer to plan the systematic production of a pool for optimum conservation of suhsurface energy. The radial flow formula advanced by Muskat' has been based on the assumption of incompressible radial fluid flow. It has been known that reservoir fluids do not behave in an ideally incompressible manner. For example, incompressible flow theory indicates a simple logarithmic relationship between the difference of the instantaneous and static well pressures when plotted against time. 'The latter stages of this type of plot of pressure build-up data generally show a marked devia-, tion from the earlier straight line trend. which deviation may be shown to be due to the compressible flow of fluids toward the well bore. Shut-in times of 24, 48. 72. or at most 96 hours are currently in wide use for determining so-called "static" reservoir pressure. Due to the continuation of compressible flow of fluids into the well bore long after this arbitrarily taken shut-in time, the determination of static pressures has almost invariably resulted in lower than equilibrium values. Materials balance calculations made early in the life of a reservoir often result in a calculated reserve which later observations prove to be too low. Failure to obtain reliable "static" reservoir pressures within the prescribed 24 or 48-hour build-up period has undoubtedly been a major factor in obtaining these low estimates. Comparison of theoretical and actual productivity performance has indicated that formation damage and not being able to attain true static pressures have been partially responsible for the observed discrepancies. Research into the theory of compressible flow behavior has resulted in methods of applying these theories to the testing of wells. Application of the developed theories to pressure build-up performance indicates that in many cases the following can be estimated. 1. The static reservoir pressure. 2. The in-place effective formation permeability away from the well bore. 3. The degree or extent by which the formation has been damaged adjacent to the well bore, either through completion methods or subsequent damage due to fluid entry. REVIEW OF THEORY Horner2 has shown that the pressure build-up within a "point source" well is approximated by the following formula: Equation (1) is the approximate "point source" solution to the radial compressible flow equation advanced by Muskat. The solution assumes the following: 1. A point source well is producing at constant rate from the center of an infinite reservoir with a constant pressure at its external boundary. 2. The fluid flowing is present in one phase only. 3. The compressibility and absolute viscosity of the fluid remain essentially constant over the range of temperature and pressure variation encountered. 4. The well i.; shut-in at the sand face arid there is 110 after production into the well bore. 5. The formation permeability is homogeneous in the direction of flow. From Equation (1) it can be seen that if an ideal well were shut-in while producing from a reservoir under the conditions assumed, the pressure build-up would be a logarithmic func-

Jan 1, 1953

By E. T. Turkdogan, W. L. Worrell

The rate of reaction of hydrogen sulfide with ferrous sulfide was studied by measuring the initial rates of sulfidation of iron strips in hydrogen sulfide-hydrogen-argon mixtures at 670°, 800°, and 900" C. The time-dependent surface sulfur activity is derived from the instantaneous rate of sulfidation with the assumption that diffusion in the sulfide layer is in a pseudo-steady state with the gas-sulfide chemical reaction. The rate of sulfur transfer from hydrogen sulfide to the surface of iron sulfide is proportional to the partial pressure of hydrogen sulfide and inversely proportional to the activity of sulfur at the surface of the sulfide layer. The derived rate equation is based on the assumption that most of the surface sites on the chemisorbed layer of iron sulfide are occupied by sulfur atoms and that the slow rate-controlling reaction is the dissociation of hydrogen sulfide on the chemisorbed layer. The experimental results are in reasonable accord with this reaction model. 1 HE slow approach to parabolic growth rate in the sulfidation of iron in hydrogen sulfide-hydrogen mixtures is a manifestation of slow approach to surface equilibrium between the gas and the surface of the sulfide layer. For example, at 800°C and Fig. 7 in Part I, the parabolic growth rate begins after approximately 1 day of sulfidation time. With decreasing temperature and decreasing partial pressure of hydrogen sulfide, the time necessary to reach gas-sulfide surface equilibrium is much longer. These observations are similar to those reported previously by Turkdogan et al.' on the oxidation of iron to wustite in hydrogen-water vapor mixtures. The slow approach to gas-sulfide equilibrium is well-demonstrated by the results in Fig. 1 where the square of the weight gain per unit area, ( g S per sq cmI2, is plotted against time for gas mixtures having PH g//>H = 1.0 with 0, 25, 50, and 67 pct Ar at 800°C. The value of 1.5 X lo-' (g S per sq cm)' corresponds to almost complete sulfidation of the iron strip (- 0.05 cm thick) to iron sulfide. The points fall on S-shaped curves. If the inflection parts of the curves are considered to be linear, thus indicating parabolic growth rate and the establishment of gas-sulfide equilibrium, their slopes would have to be the same for a fixed ratio in the gas mixture. Such is not the case, and the slopes for the "linear" parts of the S-shaped curves are lower than the value when gas-sulfide surface equilibrium is established. The subject matter of this paper is the kinetics of the surface reaction of hydrogen sulfide with iron sulfide during the early stages of sulfidation of an iron strip. EXPERIMENTAL RESULTS The apparatus and materials used were the same as those discussed in Part I. In the present experiments of relatively short duration, a purified iron strip, 5 by 2 by 0.05 cm, which was suspended in the uniform hot zone of a vertical zircon tube, reacted with a flowing gas mixture of hydrogen sulfide-hydrogen-argon. The sample was suspended from a gold chain attached to a calibrated silica spring. The amount of sulfur picked up by the iron, which formed a layer of iron sulfide, was determined by measuring the displacement of a reference point on the silica spring, using a cathetom-eter. In all cases, the degreased sample was first annealed in a stream of oxygen-free dry hydrogen for several hours to remove any impurities such as oxygen, nitrogen, or carbon which might have been present on the surface of the sample.' The rate measurements were carried out at 670°, 800°, and 900° C in hydrogen sulfide-hydrogen-argon mixtures with pH2 s/Ph2 ratios from 4 to 0.1. In a few experiments of short duration no sulfur deposition was observed in gas mixtures with (comments concerning sulfur deposition at high pH s/ph ratios were made in Part I.) Typical examples of the results obtained are shown in Fig. 2 for two temperatures and two gas compositions. With the present experimental technique, reproducible rate data could be obtained only after a uniform

Jan 1, 1969