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

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

Jan 1, 1966

By E. Martinez

The effect of ultrasonic energy transmitted through a liquid on chrysotile asbestos was investigated. Ultrasonic energy was effective in fiberization of chrysotile crudes as well as standard grades of milled asbestos fibers. Treated samples of several grades of milled fibers had increased wet bulk volumes and decreased settling and filtration rates compared to untreated fibers. Ultrasonics may be a method for fiberization of chrysotile without decreasing length or use of chemical additives that alter surface properties. Cavitation of the liquid on the surface of fiber bundles is believed to be the cause of the fiberization. It was found that ultrasonic energy greatly increased the rate of precipitation of latex on asbestos. When chrysotile asbestos fibers require additional opening or fiberization, the usual method employed is some type of high speed impact or grinding to open the fibers and produce a larger surface area. These methods always cause some degradation in length due to breaking of fibers. In addition, the efficiency of mechanical methods decreases as the diameter of fiber bundles decreases. Chemical methods have been proposed and it is claimed that fiberization down to individual fibers of 200-300 A diam is possible with some wetting agents. However, large amounts of reagent are required, approximately EDWARD MARTINEZ is with Central Research Laboratories, American Smelting and Refining Co., South Plain-field, N.J. TP 63H226. Manuscript, Aug. 12, 1963. Discussion of this paper, submitted in duplicate prior to Mar. 15, 1964, will appear in SME Transactions, September 1964, and AIME Transactions, 1964, vol. 229. 50 pct of the weight of fiber treated, and some of the wetting agent remains on the surface of the chrysotile and cannot be removed by any solvent which does not destroy the asbestos.' This investigation was directed at determining whether ultrasonic energy transmitted through a liquid would be effective in fiberizing chrysotile asbestos. Samples of asbestos crudes and commercially milled fibers were treated; settling and filtration rates of treated and untreated milled fibers were obtained. EQUIPMENT A Westinghouse Corp. ultrasonic cleaning system WEHH was used in this investigation. See Table I for a breakdown of this ultrasonic unit. RESULTS AND DISCUSSION Fiberization of Chrysotile Crudes: Samples of chrysotile crudes were pulled apart with tweezers so that coarse bundles of fiber approximately 1/16 in. in diam were obtained. The bundles were put into a bottle with 200 ml of methanol and the mixture placed into the ultrasonic tank for 30 min at a power output of 1200 w. The test was repeated using water instead of methanol. During the irradiation it was noted that the surfaces of the bundles were being fiberized. The liquid eventually became cloudy with dispersed solids. Fig. 1 is an electron micrograph of the fibers, some reduced to unit dimensions, and a fine material released by the ultrasonic energy. The platy particles in Fig. 1 were identified by electron diffraction and differential thermal analysis as brucite, Mg(OH)2, which must have been intergrown in the chrysotile crudes. Electron micrographs of bulk specimens of chrysotile have shown a fine material filling the interstices between tubular fibers.2,3 Electron diffraction patterns of the fine material collected after ultrasonic treatment indicate that it is amorphous. After decanting the solution, bundles of chrysotile remained somewhat decreased in diameter. Continuing the ultrasonic irradiation of the remaining material resulted in additional fiberization. The opening of the fibers occurred in both methanol and water. Cavitation of the liquid by the ultrasonic energy is undoubtedly responsible for the fiberization. When sound waves are transmitted through a liquid at a

Jan 1, 1963

By F. D. Richardson

STAFF: Editor, Gerhard Derge Carnegie lnstitute of Technology Schenley Park Pittsburgh, Pa. 15213 Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Jack H. Scoff, President; Richard C. Cole, Past-President; Harold 0. Emerick, President-Elect; Ralph L. Hennebach, Treasurer; Robert W. Shearman, Secretary; Donald A. Parks, Assistant Secretary; Leslie S. Wilcoxson, Assistant Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: R. E. Lund, Chairman; T. E. Dancy, H. O. Emerick, P. R. Gouwens, R. E. Grace, J. H. Jackson, H. H. Johnson, A. E. Lee, Jr., R. R. Nosh, R. D. Pehlke, and Paul Queneau. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extroctive Metallurgy Division: R. E. Grace, Choirmon; G. M. Bell, D. W. Bridges, J. M. Cigon, G. W. Heoly, T. A. Henrie, R. D. (Holli-doy, C. E. O'Neill, C. S. Somis, A. W. Schlech-ten, and Charles Shull. Iron and Steel Division: R. D. Pehlke, Choirmon; T. P. Floridis, Arnulf Muon, G. R. St. Pierre, E. T. Turkdogan, L. H.Von Vlock, and J. M. Uys. lnstitute of Metals Division: H. H. Johnson, Jr., Chairman; J. B. Clark, Vice Choirmon; M. R. Achter, G. F. Bolling. J. O. Brittoin, G. P. Conard, II, R. S. Davis, L. A. Girifolco, G. T. Hohn, J. P. Hirth, L. Himmel, G.T.horn, George Krauss, J. D. Livingston, R. D. Manning, H. M. Otte, S. V. Rodcliffe, R. E. Reed-Hill, H. C. Rogers, E. ScaIa, O. Sherby, M. T. Simnad, G. R. Speich, E. A. Steigerwald, R. A. Swolin, W. A. Tiller, W. R. Upthegrove, J. B. Wagner, Jr., Derek Wolton, H. W. Weart, W. W. Webb, and D. Published seven times yearly in February, March, April, June, August, October, and December by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc., 345 East 47th Street New York, N. Y. 10017. Telephone PLAZA 2 -6800. Subscription $30 per year for non-AtME members m United States and North, South, and Central America; $32, foreign; $7.50 for AlME members Single copies, $6.00, single copier foreign, $6.50. The AiME is not responsible for any statement made or opinion expressed in its publications . . . Copyright 1964 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AiME New York Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts. Second dost postaas poid ot New York, N. Y.,ond Ann Arbor, Mich. Volume 230, Number 6.

Jan 1, 1964

Abbey, Robert Graham, District Mgr., The W. W. Sly Mfg. Co., 50 Church St., New York, N. Y. '21 Abbott, A. N Ave. Morelos 84, Cuernavaca, Morelos, Mexico '23 Abbott, Argyle Campbell, Geol 42 Everett St., Arlington, Mass. '29 Abbott, Clarence E., V.P., Charge of Raw Materials, Tenn. Coal, Iron & R. R. Co., 1242 Brown-Marx Bldg., Birmingham, Ala. '04 Abbott, Louis Benjamin, Chief Engr., Consolidation Coal Co., Watson Bldg., Fairmont, W. Va. '15 Abeel, George H., Jr., Cons. Min. Engr 1281/2 S. Canon Dr., Beverly Hills, Cal. '18 Abel, Raymond L., Asst. Prof., Dept. of Pet. Refin., Univ. of Pittsburgh. .Pittsburgh, Pa. '28 Abel, Walter D., Cons. Engr 650 S. Grand Ave., Los Angeles, Cal. '82 Abele, Louis T., Min. & Met. Engr., Supt., Texas Hill Mine Coulterville, Cal. '31 Abell, Leo M. Millicent, S. Australia '31 Abernathy, George Elmer, Prof. of Geol. & Min., Kansas State Teachers College, Pittsburg, Kan. '20 Aborn, Robert H., Research Lab., U. S. Steel Corp. Lincoln Highway, Kearny, N. J. '19 Abozeid, Mahmood, Dept. of Mines & Quarries Cairo, Egypt '26

Jan 1, 1932

ONE DAY IN the mid-1880s, in a suburb 0f Pittsburgh, Pennsylvania, there dismounted from a train the two foremost leaders of the day in the coal and steel industries-Andrew Carnegie and H. C. Frick. Their attention was drawn to a well-loaded car of coke, which their experienced eyes recognized as a superior product. "I'll bet you that coke is from the H. C. Frick Coke Company," Mr. Frick challenged. "I'll bet it was shipped by my company." In a spirit of fun Mr. Carnegie accepted the wager. Mr. Frick lost the bet: the coke had come from M0rewood, one of three sites being operated under the direction of a young entrepreneur, Erskine Ramsay. If Mr. Frick's confidence was somewhat dented by this occurrence, the responsibility was his own. He himself had opened the way for Erskine Ramsay to become the youngest of mine superintendents; and he had dispersed all dissension regarding his choice with the words : "I'm not interested in his years, I'm interested in his record. He makes more coke in an oven than any other superintendent. And I'll take 'em out 0f the cradle if they can make coke... Suppose he is only twenty years old? ... The d --- kid is a genius, I tell you." Erskine Ramsay was to follow in the tradition of Carnegie and Frick. Not only was he ambitious and a worker his background had prepared him for it. Coal mining was in the Ramsay blood. His father, Robert Ramsay, of whom the son once stated that he had no superior as coal mining and mechanical engineer in this country, once accounted in these words for the phenomenal accomplishments which had attached to the name "It does no harm to belong to a family of mining engineers who are just as good as any in America-if it is myself that says it." Anyone acquainted with Robert Ramsay's character realized that he was not given to overstatement. And the above-mentioned Mr. Carnegie encountered young Ramsay again, a few years later in his career, and wrote of him to young Erskine's father, that he was "going to be a credit `tae us a' " (a quotation from Robert Burns.) Nor have Mr. Ramsay's achievements been identified exclusively with the industrial field in which he early asserted himself. He has been an inventor whose techniques in mining engineering have received international recognition. As an investor of foresight, he has benefitted others immeasurably, as well as himself, being an influential factor in the upbuilding of several communities in his chosen and well-loved adopted home state of Alabama since 1887. He is a philanthropist whose benefactions have run into millions, the chief beneficiaries being educational and charitable institutions. Amidst his accomplishments the lighter side of life has not been neglected and he is known for his hospitality, his

Jan 1, 1953

By R. P. Harvey, J. E. Walstrom, A. A. Brown

In view of the large number of wells directionally drilled from offshore platforms and urban drillsites, greater interest is being focused on the directional survey and on the uncertainty inherent in calculating the position of the bottom of the hole, or other benchmarks in the wellbore. Of the two methods presented here for evaluating this uncertainty, the first is analytical and uses the principles of probability and statistics. The second method uses Monte Carlo simulation to generate a pattern of the scatter of possible bottom-hole locations. Both methods are based on a model for which the usual assumption is made that the curvilinear axis of the wellbore is adequately represented by a large number, M, of linear segments joined end to end from the top to the bottom of the hole and closely following the course of the hole. The errors due to this approximation are assumed to be negligible and are not studied here. One form of the model is to consider that for a given hole there exists a perfect set of data describing it, of the above form. Each linear segment has an angle of inclination with the vertical 7, in radians, an azimuthal angle from true north xi in radians, and a length Si, in feet. The subscript variable, i, extends from 1 to M. Each of the M linear segments representing the axis of the wellbore has three components in the X, Y, and Z directions. These components are calculated from the equations: The bottom-hole coordinates as determined from the reference set of data for the wellbore are given by the following for i = 1 to M: X=SX, Y = Sy, Z=SZ; . (2) A directional survey instrument, lowered into the wellbore to the M segments, or stations, measures the values of the 7; and the 3,. In general, because of errors from various sources, the resulting angular measurements will not be precisely equal to the 7" and xi. Random variables l, and Ai are therefore considered with associated probability density functions fi(li) and gi(Ai), respectively, which represent the distributions of potential survey measurements for this hole. Since it is assumed that the values Si are accurately measured they are treated deterministically. The random variables corresponding to the surveyed bottom-hole coordinates are given, for i = 1 to M, by:

Jan 1, 1970

By T. R. A. Davey

The fundamental principles by which bismuth may be removed from lead by pyrometallurgical processes are enumerated. Qualitative discussion of the phase diagrams concerned is followed by presentation of quantitative diagrams. Brief mention is made of the practical aspects. Data presented show how chemical lead (<0.005 pct Bi) may be produced by the Jollivet, Dittmer, and Kroll-Betterton processes. BISMUTH is an element whose properties are very similar to those of lead, and its minerals are associated to a greater or lesser extent with nearly all the major lead ore deposits of the world. In consequence, the lead produced contains bismuth unless a special debismuthizing process is practiced. There does not appear to be any published comprehensive review of the effect of bismuth as an impurity on the properties of lead, and there is some uncertainty as to the beneficial or detrimental effects of small amounts of bismuth in lead used for particular applications. Standard specifications of most countries stipulate a maximum bismuth content of 0.005 pct for chemical lead. With one exception, this specification is met only by lead producers whose ores are relatively bismuth-free, or whose refineries are electrolytic. In lead for certain applications a higher bismuth content is preferred by some fabricators.&apos; In contrast to the refining for silver, copper, and antimony, the refining for bismuth does not usually result in a large overalil economic gain from the sale of byproduct. Thus, debismuthizing is customarily practiced only if market conditions demand a lead with a bismuth content lower than that produced by classical refining; i.e., softening, desilverizing, and zinc refining. Until this century, debismuthizing was carried out only a:; an incidental result of desilverizing, as later described. This century has seen the development of the Betts electrolytic process—the only successful one of many electrolytic processes proposed and patented —and a number of precipitation processes based on the pioneering work of Kroll,&apos; although only one of these, the Kroll-Better ton process,&apos; is in wide commercial use today. It is proposed in this paper to deal only with the pyrometallurgical processes, excluding those based on aqueous electrolysis. Historical Background Prior to 1833 silver (and incidentally bismuth) could not be removed from lead. To recover silver from rich bullion, the only course available to lead refineries was to cupel the bullion, forming a slag of litharge. The first slag tappings or skimmings, on reduction, yielded soft lead of very low silver and bismuth contents. Intermediate skimmings yielded a lead of somewhat higher silver and bismuth contents, which could if desired be recupelled. The last skimmings yielded a litharge very high in bismuth, which could by successive oxidation and reduction cycles be separated into high purity bismuth, and lead returns. This oxidation reduction process, with modern operating techniques, can still be used today to produce a portion of a lead refinery&apos;s output of very low bismuth content, as discussed later. In 1833 Pattinsone discovered that lead bullion could be purified of silver and bismuth by fractional crystallization, the primary lead crystals formed by partial freezing being purer than the melt. Repeated processing in pans produced a lead containing as little as 0.02 pct Bi. The simple explanation of this

Jan 1, 1957

[Chairman ZAY JEFFRIES, Vice-chairman S. SKOWRONSKI, Chairman WILLIAM M, CORSE, Secretary Executive Committee J. R. FREEMAN, JR., Local Section G. E. JOHNSON R. S. ARCHER, Non-ferrous Data Sheets P. D. MERICA EDGAR C. BAIN, Journal Committee L. W. SPRING SAM TOUR, Papers Committee F. L. WOLF H. C. JENNISON, Membership Committee Local Section Committee J. R. FREEMAN, JR., Chairman R. J. ANDERSON, Cincinnati R L. DOWDELL, Minneapolis R. S. WILLIAMS, Boston G. H. CLAMER, Philadelphia W. A. SCHEUCH, Chicago R. F, Woon, New York Papers Committee S. SKOWRONSKI, Chairman F. H. DIx, JR.-Aluminum E. R. DARBY-Bronze C. S. WITH ERELL-Copper H. A. BEDWORTH-Brass W. K. FRANK-BRONZE F. W. HARRIS-Copper R. L. SUHL-Nickel H. M. ST. JOHN--Foundry Metallurgy R. S. DEAN-Theoretical Metallurgy]

Jan 1, 1928

By L. F. Bishop

THE ore bodies of the Butte district1 are found in many different vein systems having many different structural characteristics; some are narrow with self-supporting ore but with weak walls; some are wide with weak or strong ore and weak walls; some of the veins dip steeply and others do not; some have well defined walls, and others, in the "horsetail" area, are mined to sample limits. Consequently, many types of stoping methods are used in mining these ores. The stoping methods used in the Anaconda Copper Mining Company&apos;s properties are the square-set and cut-and-fill. The square-set method is the principal stoping method used because, generally speaking, the ore and walls are weak, the ore is high grade, and good extraction is required. These square-set stopes may be classified as conventional, vertical slice, slot, timber rill, and Mitchell slice types. The conventional type square-sets are those of various shapes and sizes, mined by horizontal slicing to the boundaries of the stopes. The rock is slid to the chute and the filling is moved by gravity. The ore and waste may be handled with a scraper when local conditions require it. The vertical-slice square-set system is the type used in narrow veins that are mined in vertical panels. The slot stopes are stopes in wide veins that employ a slot across the vein instead of a con- ventional chute to handle the ore. The timber rill fs a type of square set in which the ore is mined as in inclined cut and fill but the square-set timber is used. The Mitchell slice is the type used for some broken or heavy ore blocks, or for pillar extraction between two converging slot stopes. The cut-and-fill method is used where the ore will stand without much support although the walls may be weak. The principal type of this method is the horizontal cut-and-fill, with mechanical scraping. The inclined cut-and-fill, or rill, stopes are used in some veins too narrow for scraping. The production from the various meth: ods in use for the second six months of 1944 are shown in Table I. [ ] This paper deals mainly with the vertical slice and slot types of square-set stoping, because of their effect on production locally and their potential possibilities here and in other districts, with sufficient reference to conventional square-setting for comparison.

Jan 1, 1945

By W. C. Lacy

This article is a progress report of a program designed to quantitatively evaluate geological parameters to predict stable slope angles. The author feels that, although there does not appear to be any one technique or characteristics that will suffice as an index to the determination of stable slope angles, a combination of seismic methods as outlined here, detailed geological mapping and logging of core, and a better understanding of the angle of internal friction in rock types will permit accurate estimation. A mining engineer friend once remarked, "If we don&apos;t have pit slope failures, the slopes are too flat." Since economic justification of an open pit project is based upon ultimate pit slopes, we cannot wait until the pit is developed and slopes established by trial and error. Some combination of geological and/or geophysical techniques must be developed to permit accurate prediction of stable slope angles and to suggest modification of pit outlines to result in slopes enabling maximum economic yield. This presentation is a progress report of a program designed to quantitatively evaluate geological parameters to predict stable slope angles. The principle of the weakest link applies to any slope stability evaluation and necessitates detailed geological examination and recording of observations. Physical failure will occur along any surface where shearing stress exceeds shearing resistance. Rock conditions are seldom uniform even within a single cut or pit face, so stability conditions will vary. Consequently, both plan outline and ultimate slope limits must be tailored to the specific situation. Economic advantages to be gained by slight increases in slope angles in deep pits are well recognized and stimulate efforts to obtain maximum permissible slope angles. MECHANICS OF SLOPE FAILURE Excellent reviews on the nature of slope failure have been presented+2,6,8,11 For the purpose of this study, the writer considers failure to take place by one or more of three processes: 1) ravelling, 2) translation or slope failure, and 3) rotation or base failure (Fig. 1). The effects of increased pore water pressure in soils were recognized in 1923 by Terzaghi in his development of the concept of effective stress, and he has applied the same principle to jointed rocks designating water pressure as cleft-water pressure.8 Cleft-water pressure in a rock slope reduces normal pressure on the plane of failure, thus reducing shearing resistance and resulting in slope failure. In the following discussion it is assumed that adequate drainage is supplied to prevent any build-up of water pressure. This is the first step in any program to establish maximum slopes. Ravelling: Ravelling occurs in rocks with low cohesion and entails the free movement of individual fragments ranging from single rock falls to running ground. Removal of lateral support wherever slope angle exceeds the angle of repose of the rock parti-

Jan 1, 1963

By L. F. Elkins

In 1946 Littlefield, Gray and Godbold published a thorough geologic description of the West Edmond Hunton Lime reservoir, located in Central Oklahoma, and discussion of its early performance.l They stressed implications of the nature of the reservoir rock on performance to be expected with production both by natural means and by pressure maintenance with gas injection. The essence of their analysis was that presence of an extensive interconnected system of fractures and solution channels constituting about 10 percent of the total reservoir void space in otherwise very low permeability reservoir rock would result in severe channeling of naturally encroaching water or injected gas through the fractures with little or no benefit to ultimate recovery of oil. Considerations were in progress to unitize the reservoir for pressure maintenance by gas injection. Some other engineers involved in the project had considerably different opinions at the time regarding continuity of fractures and regarding effects of such fractures on performance. The field was unitized Oct. 1, 1947. Subsequently, pilot gas injection tests were conducted in four areas of the field; large scale waterflooding was conducted in two parts of the field in the Bois d&apos;Arc or Upper Hunton; and pilot waterflooding was conducted in the Chimney Hill or Lower Hunton. Full scale water-flooding is now in progress in the Chimney Hill section where it is oil productive. The primary purpose of this paper is to divine some of the secrets of this reservoir through analysis of all aspects of its performance, with the hope that it will be of help to engineers and operators in developing and operating other low permeability fractured reservoirs. In part, this considers variance of actual performance from some widely used conventional reservoir engineering assumptions. For brevity, other aspects of unit operation and its benefits to the owners are not discussed. Oil and Gas in Place For unit participation, net pay in the Bois #Arc defined by the gross SP anomaly on electric logs totalled 2,100,000 acre-ft in the 30,000-acre reservoir. Development of West Edmond predated modem logging techniques that now would be used to determine "net" or "productive" pay. In Fig. 1 this log pick is compared with detailed core analysis and core descripfion by Littlefield et a1.l for one well identified as A on the index map in Fig. 2. Not all of the gross Bois #Arc section had oil staining, but all cores with measureable intergranular permeability were stained. (The committee selection of the Bois d&apos;Arc SP interval also includes the Frisco section as identified from cores by Littlefield.) The Bois d&apos;Arc is oil productive throughout the entire 600-ft monoclinal accumulation from the eastern upstructure erosional pinchout to the west-side oil-water contact. (See Littlefield et al.l and McGee and Jenkins for geologic detail.)

Jan 1, 1970

By S. Ramachandran, N. J. Grant, T. B. King

MANY investigations of the rate of the sulfur transfer reaction between carbon-saturated iron and blast furnace type slags have been made." It is evident that the reaction is complex, the rate being affected by the presence of elements dissolved in the metal that are readily oxidized and therefore capable of existing in the slag phase. Thus Goldman, Derge, and Philbrook- have shown that carbon, silicon, manganese, and aluminum, in order of increasing effectiveness, accelerate sulfur transfer from iron containing these elements to blast furnace type slags. Quantitative information is still, however, not available on the relation between what have been termed side reactions, such as silicon transfer and CO evolution, and the sulfur transfer reaction itself. In other words, the stoichiometry of the reaction has not been investigated. In the present investigation, the transfer of all reacting elements and the evolution of CO have been measured simultaneously in order to establish the mechanism of the reaction which occurs in practice. Information of this nature cannot be deduced from equilibrium studies. It should be pointed out that in kinetic studies of this type quantitative conclusions are applicable only to the system studied. This restriction should be borne in mind when attempts are made to compare results from different investigations. Apparatus The apparatus used enables slag and metal samples to be taken at frequent intervals and also provides a continuous record of the amount of gas evolved. A sketch of the apparatus is given in Fig. 1. It may be considered in three sections: 1) furnace section, 2) blank volume section, and 3) pressure measuring section. The furnace section is shown in detail in Fig. 2. It consists of two graphite crucibles, C and D, super-

Jan 1, 1957

By Paul Billingsley

THE purpose of this paper is a comparison, based on genesis, of the ore deposits associated with the igneous rocks of the central Montana Rockies. Considered separately, without attention to their origin, the orebodies appear to be distributed haphazard, with no fundamental laws controlling their position and character. It is believed, however, that if all the factors be weighed, this apparent confusion will to a large degree disappear. The, first essential to such a comparison is detailed knowledge of the individual mines, as to their geographic position (see Fig. 1), their mineralogical character, and in particular the derivation of their ores.1 The authors of this paper have pursued such an investigation for the past 6 years, and have accumulated a mass of evidence that enables a preliminary correlation to be attempted. It appears that the majority of ore deposits are genetically related to one or another of the igneous

Jan 4, 1917

By D. J. Coolidge, H. L. Sheakley

THIS paper does not deal with all sands used in the glass industry in Missouri; it covers only that used in the plate-glass factory at Crystal City. However, it is probably safe to say that other sands, pro- [ ] duced throughout the state for this purpose, are of identical nature. The glass sand used in Missouri is commonly called the St. Peter deposit, which is ascribed to the Ordovician Rock series in the form of sandstone. This St. Peter deposit, aside from a few small outliers, covers a large area of eastern Missouri. It forms, through a broad curve, the northeast margin of the typical Ozark region between Cape Girardeau on the southeast and Mineola, Montgomery County, on the northwest. The belt is extremely irregular, varying from one to ten miles in width; its length is 150 miles in a straight line. [ ] The outcrop near the entrance to the Crystal City mine appears in the form of a sandstone bluff approximately 30 ft. high, running along Plattin Creek (Fig. , I). Above the sand rock an overburden of Joachim limestone appears, which, thickens to nearly 300 ft. and forms the hill commonly called Buck Knob. Test holes, where drilled at various points and the drillers&apos; log indicate that the St. Peter deposit ranges in thickness from 63 to 71 feet. PROPERTIES OT THE ST. PETER SAND From an analysis of the glass sands of the St. Peter formation in Missouri, the follow-

Jan 1, 1942

By Henry M. Howe

(Cleveland Meeting, October, 1912.) Manuscript received Aug. 20, 1912. PROFESSOR RUFF&apos;S most illuminating paper&apos; describing his extremely valuable investigation of the carbon-iron equilibrium diagram assigns definite temperatures to certain very important lines in the diagram, viz.: the eutectic temperature EB (Fig. 1) and the " near-eutectic " temperature E&apos;B&apos;, but without indicating clearly enough the reasoning which warrants these assignments. These temperatures are of such primary importance that it is well to indicate the apparent gaps in the reasoning, in the hope that they may be filled in. In his diagram, Fig. 1, the point X and the lines B&apos;D&apos;HI represent the experimental results reached by Ruff and Goecke; 2 AB, AEB, and SE represent the liquidus, the solidus, and the solubility of the carbon in solid austenite in the absence of graphite according to Gutowsky,3 AB being also in accordance with Spiecker&apos;s data;4 ,S&apos;E&apos; the solubility of carbon in solid austenite in the presence of graphite according to Ruer and Iljin; 5 GS the line A3 after Goerens and Meyer;6 I and EBC the true eutectic line as inferred by Prof. Ruff from Gutowsky&apos;s data. B&apos;D&apos; is the carbon content found in cast-iron which had apparently saturated itself with carbon in the presence of the graphite of the enclosing graphite crucibles in which the determinations were made. From its straightness and its sharp inflection near 6.67 per cent. of carbon, the carbon content of * Professor of Metallurgy in Columbia University. 1 Metallurgie, vol. viii., pp. 456 to 464 and 497 to 508 (1911). 2 Idem, vol. viii., pp. 417 to 421 (1911). 3 Idem, vol. vi., pp. 731 to 743 (1909). 4 Idem, vol. vi., p. 524 (Wüst) (1909). 5 Idem, vol. viii., pp. 97 to 101 (1911). 6 Idem, vol. vii., pp. 307 to 312 (1910).

Nov 1, 1912

By R. E. Gilchrist, R. F. Nielsen

When a gas is displaced by mother in a porous medium, and there is a relative immobile liquid present. there is a transition zone in which the gas composition varies from essentially that of the original gas to that of the injected gas. The change in extent of this zone with time may be governed by a mixing process in the direction of flow and by the rate of establishment of gas-liquid equilibrium, if the gases are appreciably soluble in the liquid. The relative importance of these two factors in deterri~ining the growth of the transition zone is discussed, with appropriate equations and experimental data. INTRODUCTION The various solution methods of oil recovery involve a transfer of the components of a mixture, whether within a single phase or between a liquid and gas. The similarity of a natural porous medium to systems used in separation and chromatographic processes makes it seem reasonable that certain concepts used by chemical engineers in "mass transfer" might be applicable to petroleum reservoirs. One approach, the HETP (height equivalent to a theoretical plate), involves a distance or length of time over which equilibrium might be con. sidered as established. Another approach involves direct use of a rate of mixing or rate of establishment of equilibrium. The latter approach has been preferred in relation to production problems. DISCUSSION AND PROCEDURE When a gas or liquid in a porous medium is displaced by one of different composition but miscible with it there will be set up a transition zone in which the composition varies from cssentially that of the original fluid to essentially that of the injected fluid. If the fluid being displaced is a gas, and there is a relatively immobile liquid present, the transition zone may be

By E. B. Johnson

Cleveland-Cliffs lron Co., which operates Marquette lron Mining Co.&apos;s Republic mine, conducted a test whereby 35,000 tons of self-fluxed pellets were produced in the grate-kiln system from specular hematite flotation concentrates. A brief description of the pelletizing plant is presented along with pertinent operating details. Date is included which compare operating conditions and the chemical and physical properties of the green and fired pellets for the self-fluxing pelletizing test with the normal acid pelletizing operation. The success of self-fluxed sinter in enhancing the operation of the blast furnace during the past few years has reasonably led to the assumption that the use of self-fluxed pellets might result in even greater furnace efficiencies. A great share of development work in agglomeration has been directed towards techniques related to the production of self-fluxed pellets, but only a limited tonnage of self-fluxed pellets had been produced on a commercial scale until this past year when The Cleveland-Cliffs Iron Co. produced 35,000 tons of such pellets by the grate kiln system at the Republic mine during the period May 21-June 5, 1962. REPUBLIC&apos;S GRATE-KILN PLANT The grate-kiln pelletizing process consists of four stages, namely: feed or balling circuit, traveling grate, rotary kiln and annular cooler (Fig. 1). The balling section is conventional and utilizes four 9x30-ft balling drums in closed circuit with 5x14-ft vibrating screens having 3/8-in. rod decks. The traveling grate is 12 ft wide by 126 ft long and has 14 windboxes — six in the drying section and eight in the preheat section. The rotary kiln is 15 ft ID shell and 114 ft long. The annular cooler is 40 ft in diameter and has 12 windboxes. The cooler is divided into two zones by a moveable curtain wall. The high temperature air from the first zone is used as secondary combustion air in the kiln. Normally the only heat supplied is through the burning of No. 6 oil in the single kiln burner. Hot gases pass counter to the pellet flow through the system. The exit gases from the kiln pass down draft through the preheat section through cyclones and are drawn through the drying bed prior to exiting via the stack. The temperatures are normally held within the following ranges: Kiln 2400-2445 °F Preheat 1850-1950°F Drying 480-520°F Exit gas 200°F Pellets 120°F The design capacity of the Republic mine grate-kiln system was 2500 Itpd. Sustained production in excess of 35% over design capacity has been achieved. No screening of the cooler product is practiced. PELLETIZING TEST CONDITIONS When a decision was made to proceed with a test at the Republic mine pelletizing plant to produce 35,000 tons of self-fluxed pellets, several potential failure factors had to be carefully considered. Research work on a batch and pilot plant scale indicated that the grate-kiln system at Republic would require some major changes in order to obtain optimum conditions. In many cases compromises were agreed upon as major equipment changes and revisions were not feasible. The pelletizing conditions which laboratory development tests revealed were required in order to insure successful production of self-fluxed pellets were: 1) Good mixing of limestone and concentrate and proper moisture control; 2) Higher gas flow rates in the preheat section than are normally used; 3) Higher preheat temperatures than normal; 4) Maximum kiln temperature 2350°F. There was just cause for concern about balling problems that might occur. Approximately 10% of dry pulverized limestone was to be added to the specular hematite concentrate just ahead of the Pekay mixers on the belt feeding the balling drum. Large scale

Jan 1, 1963

By T. O. Allen, J. H. Atterbury

Laboratory and field tests during the past five years indicated considerable variation in the penetrating power of commercially available gun perforators. Many of the guns which achieved inadequate penetration in these tests have since been improved. However, recent productivity tests indicated the possibility of inadequate penetration or, at least, ineffective penetration in some wells. Laboratory experiments under simulated well conditions have demonstrated considerable plugging of the perforations, apparently as a result of factors associated with the shooting process and/or the drilling mud in the well at the time of perforating. The restrictions to flow per unit of hole depth caused by this plugging appears to be greater for jet perforators than for bullet guns of comparable diameter; however, because of the greater depth of penetration obtained with the jet guns, the total flow rates appear to he approximately equal. Limited testing with an experimental shaped charge suggests that less shot hole restriction and greater flow rates may result from larger-diameter perforations or other factors related to charge design. INTRODUCTION Gun perforating has been accepted for a number of years as a routine well completion method which is often preferred since it permits more selective operation of producing zones. Nevertheless, questions have continued to arise as to the effectiveness of the communication paths established between the productive formation and the interior of the casing. The basis for these questions has generally been failure to obtain anticipated fluid production rates through gun perforated completions in specific wells. These low productivities, together with the frequent recovery of bullets from well bores, were considered strong evidence of inadequate penetration. Laboratory investigations of the penetration performance of many of the bullet guns available as late as 1948 gave support to these indications. Subsequent electrical analog studiesl,2,3 indicated that the depth of penetration required to provide productivities equivalent to open hole was beyond the capacity of most bullet perforators evaluated in the early laboratory penetration tests. These results, together with the advent of the shaped charge in the field of oil well perforating, stimulated the interest of both oil operators and service companies in gun development. Improvements in gun design resulted in jet and bullet guns which appeared to be capable of providing sufficient penetration for most perforating jobs. However, some wells failed to yield satisfactory fluid production even after being perforated with the more powerful guns, again raising the question as to the effectiveness of the perforating operation. This fact, together with preliminary shooting into targets prepared with formation cores, indicated that factors associated with the perforating process and/or the fluids in the well bore at the time of shooting may reduce effective formation penetration and thereby decrease well productivity. These laboratory and field data prompted another phase in the investigation of the effectiveness of gun perforating: a program to determine the extent and seriousness of perforation plugging under simulated well conditions.

Jan 1, 1955

By J. C. Martin

Equations for three-phase, three-dimensional, compressible flow (including capillarity) are reduced to two-dimensional relations by a partial integration. This reduction allows three-dimensional flow problems to be treated with mathematics for only two spatial dimensions. The results can be used to formulate flow equations for two-dimensional reservoir simulators in which the effects of capillarity and fluid segregation in the third dimension are represented. Such reservoir simulators would retain many of the aduantages of two-dimensional simulators while simulating three-dimensional effects. The principal restriction of the method is that the thickness of the reservoir should be small, compared to the distance across the reservoir. INTRODUCTION In recent years, computers have been used to calculate the performances of many reservoirs. Most of the detailed calculations, however, are based on finite difference solutions of the flow equations, and present day computers are seldom able to handle a sufficient number of cells to produce entirely satisfactory solutions, even for reservoirs represented by two-dimensional arrays of cells. The situation becomes much worse when one wishes to approximate the reservoir by a three-dimensional array. A great saving in computation or a more detailed solution can be obtained for many reservoirs by using the partial integration of the equations of flow presented in this paper. The integration reduces the three-dimensional equations to two-dimensional relations; and, for studies of two-dimensional flows in vertical cross-sections, the equations are reduced to one-dimensional relations. Most reservoir performance calculations currently are based on one- or two-dimensional flow re1ations.l-3 In some cases flow in the third dimension is approximated by assuming a particular type of vertical saturation distribution, such as gravity segregation.l.2. The relations developed in this paper approach those for segregated flow as the capillary pressures approach zero, and they approach those for uniformly distributed saturations as the capillary pressures are increased. For this analysis, the ratio of the reservoir&apos;s thickness to the maximum distance across it must be small. The capillary pressures between the oil and water should also be small compared to the maximum pressure difference in the reservoir. This requirement is met by most reservoirs. It is assumed that the capillary-pressure curves are well defined, whether or not hysteresis effects are included. Also, the reservoir must have sufficient vertical permeability to allow the fluids to segregate. The results presented here provide a firm theoretical foundation to Coats&apos; et aL5 assumption of vertical equilibrium and extend the relations to three-phase flow. Coats&apos; assumption of vertical equilibrium, which he verified by calculations and experiment, is developed here mathematically from basic flow equations. DISCUSSION SATURATION AND PRESSURE DISTRIBUTIONS Appendix A presents a mathematical analysis of fluid flow in reservoirs where the ratio of thickness to maximum distance across the reservoir is small. The results indicate: (1) that the fluids along any line perpendicular to such a reservoir&apos;s upper surface are in static capillary equilibrium (vertical equilibrium); (2) that, to a first approximation, the fluid pressures and properties are functions of only areal position in the reservoir and time; and (3) that hydrostatic pressure gradients exist along any line perpendicular to the reservoir&apos;s upper surface. The results might be expected after studying several physical considerations. First, no flow is allowed normal to the upper and lower reservoir boundaries, which are relatively close together.

Jan 1, 1969

By R. C. Earlougher

Jan 1, 1970