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By L. W. Holm

Laboratory flooding experiments on linear flow systerns indicated that high oil displacement, approaching that obtained from completely miscible solvents, can be attained by injecting a small slug of carbon dioxide into a reservoir and driving it with plain or carbonated water. Data are presented in this paper which show the results of laboratory work designed to evaluate this oil recovery process, particularly at reservoir temperatures above 100°F and in the pressure range of 600 to 2,600 psi. Under these conditions CO2 exists as a dense single-phase fluid. It was found that a bank, rich in light hydrocarbons, was formed at the leading edge of the CO? slug during floods on long cores. Formation of this bank is probably due to a selective extraction by the C02 and, it is believed, partially accounts for the attractively high oil recoveries. In crddition to the efficient displacernerlt of oil from the pores of the rock by this process, the favorable rnobility ratio related to a C0 2-water flood also contributes to high oil recovery. A further advantage of this process is noted on limestone and dolomite rock, in that the CO1 reacts with the porous medium increasing its permeability. Flooding experiments were conducted on sandstone and vugular dolomite models. The results of this experimental work show the effect on oil recovery of type of porous medium, pore geometry, flooding length, and flooding pressure. The porosity of the cores and rilodels varied from 16 to 21 per cent and their pern~eabilities ranged from 100 to 200 md. A reconstituted West Texas reservoir oil, a West Texas stock tank oil, an East Texas stock tank oil and Soltrol were used to represent reservoir oils in this study. Oil recoveries ranging from 60 to 80 per cent of the original oil in place in these cores were obtained by CO2,-carbonated water floods at pressures between 900 and 1,800 psi, compared with conventional solution gas drive and water-flood recoveries of 30 to 45 per cent on the same cores. Oil recoveries greater than 80 per cent resulted frorn f1oods at pressures above about 1.800 psi. There high recoveries were noted from both the sandstone and the irregular Porosity carbonate cores. In all floods, additional oil was recovered by a solutiorr gas drive resulting from blowdown following the flood. Oil recoveries of 6 to 15 per cent of the original oil in place were obtained during this blowdown period. This additional recovery was found to be a function of oil remaining after the flood, decreasing with decreasing oil saturation. It was also noted that highest oil recoveries by blowdown were obtained when carborlated water rather than plain water followed the CO, slug. INTRODUCTION Miscible phase or solvent flooding processes, which are designed to increase oil recovery -from petroleum reservoirs, involve the injection of small quantities of a petroleum solvent into the reservoir, followed by an inexpensive scavenging fluid which is miscible with the solvent. Essentially complete displacement of oil from the pores of reservoir rock has been obtained by this technique. CO,, although not completely miscible with most reservoir oils at moderate pressures, is highly soluble in these oils at pressures above about 700 psi; there is appreciable swelling and reduction in the viscosity of oil when CO, is dissolved in it. Therefore, CO, could be expected to perform similarly to other oil solvents as a displacing agent. CO, is also highly soluble in water at elevated pressures, so water should be a satisfactory material to drive a slug of CO, through an oil-bearing reservoir. A favorable mobility ratio would be obtained through the reduction in viscosity of the oil and the use of water as a final displacing agent. A number of investigations of the use of CO, to improve oil recovery have been reported in the literature.2,3,4,5,6 These studies, however, have been conducted on uniform porosity sandstone at relatively low temperatures and pressures. The behavior of CO1 as a flooding agent at temperatures above its critical temperature could not be predicted adequately from these studies, particularly for the case of non-homogeneous rock. The purpose of this work was to evaluate the oil recovery efficiency of a process involving the injection of a CO2 slug followed by carbonated water, at reservoir temperatures above 100°F and in the pressure range of 600 to 2,600 psi, and to compare this process with conventional water flooding. The investigations were primarily designed to provide information on the efficiency of the process in irregular porosity carbonate rock. The effects of flooding path length, the presence of free gas, the type of oil to be recovered, and the amount of solvent required were also determined. The essential results of static phase behavior studies and experimen-

By P. T. Stroup

Jan 1, 1964

Jan 1, 1920

By A. H. Larson, R. J. McClincy

Laboratory-scale decopperizing experiments with multiple sulfur addifions were conducted at 330°C on ternary Pb-Cu alloys containing, as the third elenlent, Sn, Ag, As, Sb, Bi, Zn, and Au, common impurities in lead blast-furnace bullion. For silver and tin, an increased rate and extent of 'cofifier removal was obsert3ed. The elements As, Sb, Zn, Au, and Bi had no effect or less effect as compared to sulfur additions with no i)npurily additions. THE production of primary lead in the blast furnace yields an impure lead frequently containing such impurities as copper. antimony. arsenic. tin, gold, silver iron, oxygen. and sulfur. By cooling this lead to a temperature near its melting point. most of the iron, sulfur, and oxygen and part of the other impurities are removed in the form of a dross. With incipient solidification of the lead, the copper concentration wil have been reduced to 0.02 to 0.05 pct. depending upon the concentration of the other impurities. according to Davey.' Since copper interferes with the treatment of silver after the desilverizing process, it is desirable to decrease the copper content of the lead still fur-ther before the lead is desilvered. The decopperizing of the lead is accomplished by stirring a small quantity. approximately 0.1 pct. of elemental sulfur into the lead at a temperature near its melting point, 330" to 360°C. The copper is removed as a copper sulfide which constitutes a small fraction of a voluminous dross consisting mostly of lead sulfide and entrained metallic lead. The residual copper concentration following the decopperizing operation is frequently as low as 0.001 to 0.005 pct. Thi fact has aroused considerable interest because the equilibrium copper concentration of lead in contact with solid PbS and solid Cu2S is at least an order of magnitude greater, 0.05 pct Cu at 330C. 1, 2 Most investigators have suggested that various impurities in the lead bullion are responsible for the very low copper concentrations frequently encountered in practice. There is little agreement, however? as to which of the impurities are helpful and which are not.3"11 Also. few investigators have sought to explain the mechanisms responsible for the removal of copper to very low concentrations. Willis and Blanks9 have proposed that a nonstoichiometric copper-deficient cuprous sulfide forms in place of the supposed Cu2S. Being copper-deficient, this sulfide phase would possess a low copper activity, and the diffusion of copper dissolved in the liquid lead into this phase would be greatly facilitated. Pin and wagner2 have investigated the removal of copper from liquid lead by studying the effect of impurity-doped lead sulfide on the decopperizing of pure Pb-Cu alloys. Samples of the doped PbS were held in contact with copper-saturated lead for 1 week at 33'7°C. They reported a beneficial effect on decopperizing with bismuth and antimony and no effect with tin or silver. which is directly opposite to the results observed in practice and those reported by Davey 3 and this studv. The purpose of this paper is to describe the effects of certain additive elements on the extent to which copper can be removed fro111 liquid lead by successive additions of sulfur. The impurity elements were added individually to prepared Pb-Cu alloys. The resulting ternary alloys as well as a binary Pb-Cu alloy were then decopperized with repeated additions of sulfur. EXPERIMENTAL Materials. Granulated test lead with a purity of 99.999 pct and the additive elements Cu. Ag. Sb. Bi. Zn. Sn. and Au with purities of 99.99 pct were American Smelting and Refining Co. research-grade materials. The major impurities in the lead were 1 ppm each of iron and copper. all others being less than 1 ppm. The arsenic used was a technical-grade arsenic of 98+ pct purity. Reagent-grade flowers of sulfur were melted under argon to provide small pieces free of fines. Apparatus. The decopperizing experiments were carried out in a 25-mm-OD by 375-mm-long Pyrex tube sealed at one end. The tube was mounted vertically in a resistance-heated. hinge-type tube furnace controlled to within ±lcC. Temperature measurement was accomplished by means of a standardized chromel-alumel thermocouple sealed into the base of a silica. paddle-type stirring rod. All decopperizing experiments were carried out under an argon atmosphere. Procedure. A Pb-Cu starting alloy containing 0.05 pet Cu was prepared under carbon and poured into cold tap water to produce shot. The ternary alloys were prepared by melting together 100 g of the starting alloy and a sufficient amount of the impurity element to yield the desired concentration. The resulting alloy was then homogenized in a Pyrex tube at 450C with continuous stirring. The furnace temperature was then lowered to the operating temperature of 330°C. When thermal equilibrium had been obtained at the operating temperature, individual additions of 0.2 pct (0.2 g) of solid sulfur were added to the melt and stirred in. Stirring was continued for a period of 3 min. discontinued for 5 min. and resumed for the remaining 2 min of a 10-min cycle. This cycle was repeated for as many sulfur additions as desired. When the decopperizing experiment had been completed the lead bullion was quenched and samples of the bullion and dross phases were taken for analysis. Results. The results obtained in the decopperizing

Jan 1, 1970

Jan 1, 1886

By H. H. Keller, E. J. Couch

Damage to production wells subjected to the high temperatures associated with in-situ combustion projects has been a problem since the advent of this thermal recovery technique. Injection of water down the annulus of hot wells has been successfully utilized for cooling and prolonging the life of such wells. A mathematical model that is suitable for predicting the effectiveness of cooling water in a particular application is developed. Typical results for practical ranges of the various parameters involved are presented. INTRODUCTION In the normal course of in-situ combustion operations, highly damaging conditions develop in the production wells as the combustion zone approaches, and these wells are subjected to high temperatures (up to 1500F). The resulting well damage is recognized as one of the more serious operating problems unique to the in-situ combustion process. Even in operations where well completions have been specifically designed to cope with this problem, the question arises as to how this destructively high temperature can be kept within tolerable limits. A simple and economical approach to this problem is to circulate cooling water down-hole. This method has been used with some success in shallow reservoirs. At greater depths, however, the heat exchange with the overburden surrounding the well and between the fluids in the tubing and the annulus tends to equalize the temperatures of the two fluid streams so that the cooling capacity delivered to the bottom of the hole decreases with well depth. This method would provide no appreciable control over the bottom-hole temperature at great depths. In order to delimit the condition under which cooling by water circulation is effective, the wellbore temperature must be related to the water inlet rate and temperature; to the reservoir depth, production rate, and initial temperature; and to the combustion at at bot tom-hole depth. A model that meets these requirements and that will offer an approach for developing engineering solutions to practical design and operating problems is described in this paper. MATHEMATICAL MODEL Previous studies of temperature distributions include those for flowing wells1p2 and those for hot fluid injection. Adams and Haddenhorst 6 presented solutions for the down-hole circulation of hot oil in the treatment of paraffin-deposition problems. In this paper the thermal model presented by Ramey 4 is adapted to the flow system shown schematically in Fig. 1. Water at temperature Ti is injected at a rate wi and flows down the annulus outside the tubing. It mixes at bottom-hole depth D with the fluids produced at race w from the hot reservoir at temperature T. This mlxtureJ. of injected water and reservoir fluids flows up the tubing and is produced at the surface at TI,. In order to describe the temperature response in this system, we make use of the usual conservation of

Jan 1, 1969

By G. S. Rice

IT is evident from Professor Louis' remarks that he holds a different opinion on certain phenomena connected with a specific type of surface subsidence from mining than is held by many engineers in the United States. The question which appears to be at issue is whether or not the line or plane of "draw" produced in ground movement resulting from extraction of pillars may, under certain conditions, be vertical or even inclined toward the workings rather than inclined for- ward over the unworked mineral, as it is universally agreed occurs in mining by the longwall advancing method. In discussing this case it is well to take the simplest condition, such as specified by Professor Louis, of a flat bed, whether it be coal, iron or other mineral, where the overburden is stratified rock and where there is no overlying quicksand. Professor Louis says in effect that his experience is that the ultimate angle of draw is always positive and inclined 5" to 15" from the perpendicular over the unwrought mineral. My experience under Illinois coal-mining conditions is that .'where longwall advancing is used the draw is always positive as Professor Louis describes it, but that in extracting of panels by withdrawal of pillars, the ground movement is manifested, after the first roof' beam break, by the forming of an unstable dome over the goave. Then subsequently, by the falling of individual slabs from the under side, the dome gets larger and higher until it breaks through to the surface of the rock., Up to this time, arch stresses buttress the rocks above the solid coal or mineral. When, however, after. the dome breaks through and the central hole - #enlarges so the arch is no longer sufficiently supported -the stratified rocks cantilever out .from over the solid unworked mineral and tend to break off in masses triangular in vertical cross-section, until the broken loose material, sliding down against the solid rock, .has such a thrust that it balances the tendency ,for the solid stratified rock to break away and slide toward the excavation.

Jan 1, 1929

By Paul H. Hunt

MANY MISUNDERSTANDINGS have arisen regarding -Al the purchase by the Government of 24,000,000 oz. of domestically produced silver annually for the next four years at a price of 64 1/2c. to the producer. Some editorials have an¬nounced rather sarcastically that be¬cause of the strong western silver bloc in Congress, the Administration is paying a bonus of approximately $22,000,000 to a few large silver produc¬ers of the West, the amount being figured on the total purchase of about 100,000,000 oz. and the difference between the Government price and the world price for silver. Actually the Government will make a profit on this purchase, due to seigniorage, of something over $60,000,000. The 96,000,000 oz. of silver, for which the producers will receive approximately $62,000,000, will be produced in association with at least $100,000,000 worth of lead, zinc, copper and gold; the greater part of this $162,000,000 worth of metal will be produced at little profit to the mining companies, as will be shown later, because of the low prices for lead, copper and zinc. This amount of money will be spent largely for labor and supplies, thus greatly relieving the national burden of unemployment. Certainly, western mining, in the purchase of this silver, is not victimizing the Federal Government.

Jan 1, 1934

By Harrison Souder

In view of the proposed visit of the Institute to Cuba this winter, the following brief sketch of the principal mineral deposits near Santiago de Cuba has been prepared largely from notes taken in February, 1903, during a visit to the mines then in operation in the province of Santiago de Cuba. Westward from Cape Maysi, the most eastern point of the island, the coast is rocky and uninviting. The usual course of the steamers is well in toward the shore, and the lines of stratification of the rocks can be distinguished clearly, the presence of iron or other ores being indicated by frequent blotches of mineral stain. One is impressed with the general rugged character of the southeastern coast-line,—an almost unbroken barrier of coral-limestone bluff's, full of caves and hollows, into which the surf rushes with a roar and bursts into tall fountains of spray. Beyond rises abruptly the Sierra Maestra range, whose sharp, peaked crest-line betrays its eruptive or igneous origin. From a height of about 800 ft. near Cape Maysi, this range gradually rises to the westward, attaining its maximum elevation of more than 8,300 ft. in the Pico Turquino, beyond Santiago. A general resemblance to the mountain-ranges of southern New Mexico is noticeable. At Daiquiri, 20 miles east of Santiago harbor, the extensive

Jan 1, 1905

By Milton E. Wadsworth, Daniel B. Brimhall

Column leach studies of a low-grade porphyry copper ore were made. The technique used involved alternating oxygen absorption and copper leach cycles. The leach solution was displayed from the column with oxygen. The volume of oxygen reacting with the ore was measured with a gas burette. The copper released as a result of exposure to oxygen was correlated with the oxygen uptake. The oxidation rate was found to be dependent on the pH of the solution wetting the particles and was markedly increased by increasing the temperature of the system. Decreasing the particle size of the sample increased the oxidation rate. A material balance on the system indicated 1 mole of oxygen yielded in excess of 1 mole of copper in solution. A discussion of the important parameters is presented and the results are related to dump leaching in general.

Jan 1, 1974

By G. G. Waddell, T. J. Crocker, S. S. M. Chan

A successful engineering structural design often depends upon a thorough understanding of the material properties of the structure. It is no exception when designing a supporting system for stable underground openings. For this reason, studies were made in the deep mines of the Coeur d'Alene mining district to obtain engineering properties of rocks and rock masses immediately surrounding underground openings. In this paper, data concerning laboratory tested physical properties of rocks and in-situ deformation behavior of rock masses from the Galena, Lucky Friday, and Silver Summit mines of the district are presented. Interpretations of the data so obtained and suggestions for the use of the results of the investigations as design criteria are also outlined.

Jan 1, 1973

By W. D. Forgeng, B. F. Decker

IT has been known for almost a century' that silicon and nitrogen combine when heated to a high temperature. Three nitrides have been reported, SiN, Si3N,, and Si,N, containing 33.3, 40.0 and 42.9 pct nitrogen by weight, respectively. The existence of SisN, is well established but that of Si,N, and SiN is doubtful. The first systematic study of the reaction between silicon and nitrogen was made in 1910 by Weiss and Engelhart" who determined the rate at which silicon absorbed nitrogen at temperatures from 1250°C to

Jan 1, 1959

By J. M. Flaitz, A. S. Parks

OF the various methods of sampling gas-condensate wells, a method that secures a continuous representative sample of the well stream is desirable. Such a method, consisting of a sampling tube introduced into the well tubing, has proved satisfactory. The method is sufficiently accurate for operating and engineering problems. A portable testing apparatus can be used with the sampling tube to obtain data useful in studying the economic and technical aspects of the development and operation of gas-condensate properties. INTRODUCTION The recent discovery and development of gas reserves that contain hydrocarbons that condense with reduction of temperature or pressure, or both, to form a product known as condensate, has brought many new problems to the oil and gas industries. With further discovery of deep, high-pressure fields it is presumable that many more gas fields of this type will be added to the steadily increasing number. Such gas reserves are found either associated with oil as a gas cap or in separate formations. There seems to be no positive correlation between the physical or geological nature of the reservoir, and the chemical composition or phase characteristics of its contents. Knowledge of the chemical make-up and phase behavior of gas-condensate reserves are needed to cope with many problems. A knowledge of the chemical composition and phase characteristics of the reservoir material is necessary to properly design a gasoline or recycling plant, to estimate natural gas and condensate reserves, to enable the operator to study the economic and technical aspects of various methods of operation and development, and to carry out the plan of operating subsurface and surface lease equipment. This information is often useful in questions of mineral ownership, proration, legal position, and taxation. It is the purpose of this paper to discuss methods used by the writers to determine the chemical composition and phase characteristics of the fluids produced from a condensate well. The scope of the paper includes a discussion and description of the method of sampling, the results of tests on the accuracy of the sampling method, a description of a portable testing apparatus used to examine the phase characteristics, typical results of tests on wells from several condensate fields, and some of the applications of these data to production problems. References to previous work on this subject are cited at the end of the paper. THE PROBLEM At reservoir conditions of temperature and pressure, the fluids produced from a condensate well exist in a homogeneous vaporous condition. The consequent reduction of temperature and pressure that occurs as this gas enters and flows up the well tube results in condensation of some of the hydrocarbon material to form a liquid. The relative amount of liquid condensed at any point in the flowing system

Jan 1, 1941

By N. J. Myers, S. J. Nemeth

POWER in the mill at Appalachian Sulphides Inc. is provided by 86 electrical motors ranging from 1 to 200 hp and totaling 1200 hp. After a careful study of different types of support for these cables an expanded metal trough was chosen as the most suitable. One hundred and twenty feet of trough were installed in 18-in. width and 150 ft in 6-in. width. This trough carries all the power as well as the control circuits. Now that the electrical distribution system is complete it is clear that this type of cable supporting system offers many advantages. To handle the same amount of cable in conduit, for example, would have required such a jungle that wiring all the different motors and controls would have been very difficult, even for the original hook-up. In the Appalachian Sulphides operation it has been necessary to make changes from time to time in the wiring of the different motors. These changes are readily made with the present cable supporting system because the trough leaves the wires accessible for rerouting as needed.

Jan 1, 1958

By William E. Milligan

SELENIUM and tellurium occupy adjacent positions in the odd division of group VI of the periodic table immediately below sulfur, with atomic numbers 34 and 52 and with atomic weights of 78.96 and 127.61 .† A recent investigation has indicated the figures in Table 1 as the order of natural abundance of their isotopes. [ ] Experimentally, as a result of bombardment, many additional isotopes have been produced and studied. They are characterized by a relative short half-life. The elements of group VI in the periodic table are of great in-

Jan 1, 1953

Jan 1, 1925

Jan 1, 1969

Jan 5, 1953

By Frederick M. Becket, Russell Franks

In a recent article,l which described the softening effect of columbium in plain high-chromium steels, the authors stated that their investigations had shown columbium to be also a particularly valuable inhibitor of intergranular corrosion in steels of the 18 per cent chromium, 8 per cent nickel type. It is the purpose of the present paper to record some of the results obtained through the introduction of columbium to the austenitic chromium-nickel steels. The damaging effects of this type of corrosion have become so widely known as to restrict considerably the applications of the steels under consideration, and therefore there is little question of the importance of the goal to be attained. Numerous contributions concerning the susceptibility of the austenitic chromium-nickel steels to intergranular corrosion have appeared during the past few years, and among others who have dealt constructively with the subject are such well-known authors as Strauss and Houdremont of Germany, Hatfield of England, and Bain in the United States. Different theories have been propounded as to the cause of intergranular corrosion, and various remedial measures have been proposed, the majority of which involve the use of addition agents. Titanium is the addition agent at present most generally employed, as suggested by Houdremont and modified as described by Bain, Aborn and Rutherford. Little has been published on the effects of holding these steels for long periods at the relatively lower temperatures in the presence of corroding media, and the effects have mot been fully realized by producer and consumer.

Jan 1, 1934

By Hallet R. Robbins

Korea, the ancient" Hermit Kingdom," is a peninsula jutting out from the coast of eastern Asia. By the natives it is called " Chosen," nfhich, translated, means " Land of the Morning Calm." It lies between the Yellow sea and the Sea of Japan. On the north it is separated from Manchuria and the Russian province of Primorsk by the Yalu and Tiumen rivers; on the south the Korcan straits interpose a rough voyage of 120 nliles to the nearest point in Japan. The entire country is situated between the parallels of 34O and 42O N. latitude. The surface of the country is made up of successive ranges of ul~glaciated mountains, separated by narrow, fertile, and more or less densely populated, valleys. Through all the obscure centuries of its history, Korea has succeeded in maintaining a monastic seclusion, over which, from time immeniorial until the late Chino-Japanese war in 1894, China exercised a shadowy sovereignty. Although Korea had been forced into slight foreign contact previously, her first forcign treaty was signed with Japan in 1876. Under the restraining guardianship of China, the Japanese treaty bore but infiignificant innovations for Korea; but when, in 1883, a treaty was made with the United States, the first of the western nations, a decade after the American gunboats, under Commodore Rodgers and Lieutenant Schley, forced their may up the Salee river, Korea awoke from her sleep of 4,000 years. The Eorean peninsula suddenly became the arena where the enterprises and individuals of many foreign nations met in fiercest rivalry. Out of this struggle grew two singularly successful American enterprises, both of which have played an important part in developing the natural resources of the country. The first, and best known of these, is the Oriental Consolidated Mining Co., which was organized by Lcigh Hunt

Jan 1, 1909