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By Donald L. Katz

The compressing of gas into a partially depleted gas drive oil reservoir to bring the contents to a single phase miscible with gas is proposed as a process worthy of serious study. The compressed gas and vaporized oil would be recovered by cycling. This paper explores the Possibility of recovering oil from reservoirs of 6,000 ft or more by this method. INTRODUCTION Many new methods for increasing the recovery of oil from reservoirs are under consideration in the various research laboratories. One method which should be considered for recovering oil From partially depleted gas drive fields is to compress gas into the reservoir until the contents become a single phase miscible with more gas. Natural gas then may be cycled through the reservoir to recover the oil. This procedure ideally will eliminate the capillary effects of the liquid ill the porous media and should permit recoveries similar to those obtained in cycling operations, probably of the order of 80 per cent. This paper explores the information now available for the prediction of the performance of such a project and discusses the problems likely to be encountered in recovering oil by cycling. For many years dry natural gas has been passed through oil reservoirs to recover natural gasoline which would vaporize from the oil. Recently a process of recovering more of the high boiling hydrocarbons has been described by employing high pressures at which the heavier hydrocarbons have a higher volatility. Nevertheless. this reported method does not eliminate the differential nature of the vaporization process and capillary forces are still present in the reservoir. The process under discussion in this paper would minimize differential vaporization and would remove capillary forces which are responsible for low oil recoveries. Higher gas pressures are required to accomplish this removal of the miniscus, but it does not follow that more gas is required for oil recovery. The process is limited to reservoirs deep enough to permit the use of the required pressure — Probabably 6,000 it and deeper. DESCRIPTION OF THE PROCESS Briefly, the process is to compress natural gas into an oil reservoir which is partially depleted so that it has an oil saturation in the range of 40 to 60 per cent of the hydrocarbon pore space. The injected gas will pass through the channels formerly carrying gas to the wells to build up the pressure and dissolve in the oil phase. This injection will continue without production from the field until the reservoir reaches a single phase. If one were to select unique conditions such that the gas composition, the reservoir oil composition and the Per cent saturation would bring the mixture in the reservoir to the critical temperature and pressure simultaneously the phase behavior accompanying injection is shown by Fig. 1. The oil-gas mixture in the depleted reservoir has a critical temperature at C,. Addition of natural gas to the mixture will give a new critical temperature for each addition. Mixture No. 3 is shown to have its critical temperature at the reservoir temperature and reservoir pressure at P: the critical pressure. Under ideal behavior, the entire reservoir would be at iti critical temperature and pressure and the entire hydrocarbon content would be at a single phase. If the reservoir content were a binary system of methane and a heavy constituent. it would be miscible with more methane. However, for complex mixtures the critical locus does not confine the two phase region, and the dew point curves of Fig. 1 occur above the critical locus. If fluid which was injected into the rezervoir at the critical point were of the

Jan 1, 1952

By Frederic E. Carter

THE gold, silver, copper alloys have been the subject of several fairly complete investigations by Jänecke, Sterner-Rainer1 and others, and indeed it would seem as if almost too much labor had been expended on them when one thinks of the numerous other ternary alloys calling for more light; however, the combinations of the three metals are actually so widely used in jewelry that they merit perhaps the work done on them. There are a few properties of importance and interest not treated by the authors mentioned which the writer investigated some little time ago, and therefore he has ventured to put on record the results of some of his tests made at that time. He has chosen, as being the two series of most importance to the jeweler, only the 14 and 18-kt. golds, so the subject is by no means so inclusive as that previously treated. As stated, this paper is merely a record of tests made in a practical manner on two useful series of alloys, and is not at all a critical study of their properties. 14-KARAT ALLOYS These alloys are important because they are the most generally used in 14-kt. jewelry; by changing the proportions of silver and copper there are obtained all shades of color from the green of the alloy containing gold and silver but no copper, to the red of the alloy containing gold and copper but no silver. Many 14-kt. gold alloys are made with the addition of zinc to the three metals mentioned here; the added metal does not appreciably alter the color of the alloy nor has it, in general, much effect on the working properties; it may, however, prove useful as part of the zinc added may act as a deoxidizer and render the alloy free of gas. It is not a necessary addition because with proper precautions all the 14-kt. gold alloys containing only silver and copper in addition to the gold can be made free of gas and capable of being cold rolled without cracking. The alloys in which approximately equal quantities of silver and copper

Jan 1, 1928

By T. H. Alden, H. W. Schadler

The strain rate dependence of the flow stress of the eutectoid Zn-Al alloy has been determined as a function of mechanical processing, microstructure, and temperature. The best superplastic properties result from the ultrafine, equiaxed structure produced by solution treatment and isothermal transformation at 0°C. Lamellar structures produced by isothermal transformation and coarse equiaxed structures produced by annealing also exhibit strain rate sensitivity in excess of 0.5, but at higher stresses and lower strain rates than the finest structure. Solution treatment and isothermal transformation eliminate the effect of prior processing history. Small composition variations in the binary alloy do not influence the mechanical properties. Below the eutectoid transformation temperature (.275C) increasing temperature lowers the flow stress at all strain rates. The data do not favor any of the present proposals for the mechanism of superplastic flow. ALLOYS of zinc and aluminum, near the eutectoid composition, have been investigated for: 1) the flow stress-strain rate and elongation behavior,1, 2) the transformation kinetics,3 and 3) structure,3"5 but the structure sensitivity of the mechanical properties is poorly understood. Using a near eutectoid alloy water-quenched from 380°C, Backofen et aL2 estab- high and increases with increasing strain rate. They found a correlation between strain rate sensitivity and tensile elongation as expected from the increased resistance to necking that a high strain rate sensitivity provides.296 The large elongation at high strain rates is attractive for metal forming. Since most other superplastic alloys7-l3 do not show high strain rate sensitivity at such a high strain rate (for the exception see Ref. 12) there is the possibility of a unique deformation mechanism for this alloy. The sensitivity of the mechanical properties of the eutectoid alloy to thermal history1 suggests a structure sensitivity that has not been demonstrated. Gar-wood and Hopkins3 identified a lamellar product for material transformed between 200" and 260°C. The size of the lamellae decreased with decreasing temperature. They also demonstrated that an unresolved transformation product formed below 200°C. A granular two-phase material was resolved for specimens quenched to below 150°C by Mitbauer and sauerwald4 who observed coarsening of the structure after annealing. The role of grain boundaries in superplastic deformation is suggested by the strong effect of grain refinement in encouraging this phenomenon at high strain rateS7-11, 13 and is emphasized in several proposals about rnechanism7, 8, 12 and in a theory14 of high-temperature deformation. Alden8 showed metallographic evidence that grain boundary sliding is occurring extensively at strain rates where m is large but less at high strain rates where normal plasticity is observed. Holt and Backofen10 have shown that sliding also oc-

Jan 1, 1969

By Walter White

THE measurement of the reading of a thermoelement is the measurement of an electromotive force extraordinarily small compared to those generally used in commercial work. Of the various possible methods of measuring such a quantity, the most advantageous is always a delicate galvanometer. Since a galvanometer measures current, it is necessary to adopt some scheme by which its current reading shall indicate electromotive force. There are two general methods of doing this. One is to use the delicate galvanometer as a "direct reader," that is, to let the electromotive force of the thermoelement furnish the power and produce the current measured. If the resistance is constant the reading will, after a suitable calibration, give the electromotive force of the thermoelement which, by means of a table or of a suitable scale in the galvanometer itself, will FIG. 1.-SIMPLIFIED POTENTIOMETER. POTENTIAL DROP ACROSS THE PART PIN or CIRCUIT OF BULL CELL BALANCES THAT OF THERMOELEMENT TC WHEN GALVANOMETER G READS ZERO. give the temperature. The other method, that of the potentiometer, is to balance the electromotive force of the thermoelement by means of another electromotive force, using the galvanometer to tell when the balance is made. The usual way of getting this other electromotive force is to have a battery, the "bull" cell, send a current through a series of resistances, which 'may in a special case be the resistance of a single wire. The fall of potential along this circuit will then, by Ohm's Law, be proportional to the resistance; the potential difference between any two points, proportional to the resistance between the two points. This is represented in Fig. 1, where M and N are the two points in the circuit AZ of the battery. If M or N, or both, is movable so that the resistance

Jan 9, 1919

By Eugene McAuliffe

THE Coal Division undertook its most ambitious program this year at the New York meeting, with six full' sessions and a luncheon on Monday which had a record attendance and at which the newly elected officers for the Division were announced. Eugene McAuliffe, president of the Union Pacific Coal Co., Omaha, Neb., was unanimously selected as Chairman; J. B. Morrow, preparation manager of the Pittsburgh Coal Co., as Vice-Chairman; and H. E. Nold, Ohio State University, Secretary. During the past year two new and interesting activities were conducted by the Division directed at stimulating the interest of junior and student members. Reports were presented at the luncheon meeting by the chairmen of these commit¬tees. J. B. Morrow. chairman of the paper prize awards, and H. N. Eavenson reported on the work of the mining machinery manufacturers fellowship, the work on which was completed the first of the year. Several excellent papers are expected from these two groups for the next meeting of the Division to be held in Pittsburgh some time in the fall. The regular six-session program was filled from start to finish with interesting papers and much discussion, but unfortunately not enough time for the latter. The papers covered the field of prospecting, mining methods, preparation, utilization, mechanization, and safety, and all through the program we were constantly reminded of the value and need of research in the coal industry.

Jan 1, 1936

By W. A. Clark

The production of sand in an oil well increases operating costs because of abnormal wear in subsurface equipment, the necessity for frequent cleanouts, and the need for a means of disposing of the sand. Moreover, removal of sand from the zone can bring about the creation of cavities from which bodies of formation, sand or shale, may slough into the hole, endangering the shutoff, impeding production or collapsing the liner. The procedure known as gravel packing is attracting attention as a means of controlling these factors and contributing to the productive life of a well. That gravel packing is now substantially beyond the preliminary stage on the Pacific Coast is reflected in the 191,000 bbl. of oil produced monthly by the 66 gravel-packed wells in 11 different producing sectors. Reasons fob Gravel Packing Gravel packing, if properly carried out, can be expected to provide the following benefits: 1. Prevent the movement of sand and thus eliminate sand production and sand fills, and prevent the formation of cavities. 2. Provide a practical, relatively inexpensive, large-diameter hole, which will provide well-known theoretical advantages. 3. Support the walls of the hole by completely filling the space between the liner and the formation, regardless of its irregularities, and afford a support for liners. 4. Provide for more efficient pumping operations in wells by: (a) possibly utilizing the gravel as a gas trap in pumping gaseous fluids, (b) allowing deep submergence of the pump into the oil zone. In a conventional well—that is, where the liner is set in an open hole-. even though perforation sizes are chosen according to known rules based on analysis of sand grains from samples from the zone, there is likely to be some production of sand. This may be due to the miscalculation of

Jan 1, 1940

By W. A. Clark

The production of sand in an oil well increases operating costs because of abnormal wear in subsurface equipment, the necessity for frequent cleanouts, and the need for a means of disposing of the sand. Moreover, removal of sand from the zone can bring about the creation of cavities from which bodies of formation, sand or shale, may slough into the hole, endangering the shutoff, impeding production or collapsing the liner. The procedure known as gravel packing is attracting attention as a means of controlling these factors and contributing to the productive life of a well. That gravel packing is now substantially beyond the preliminary stage on the Pacific Coast is reflected in the 191,000 bbl. of oil produced monthly by the 66 gravel-packed wells in 11 different producing sectors. Reasons fob Gravel Packing Gravel packing, if properly carried out, can be expected to provide the following benefits: 1. Prevent the movement of sand and thus eliminate sand production and sand fills, and prevent the formation of cavities. 2. Provide a practical, relatively inexpensive, large-diameter hole, which will provide well-known theoretical advantages. 3. Support the walls of the hole by completely filling the space between the liner and the formation, regardless of its irregularities, and afford a support for liners. 4. Provide for more efficient pumping operations in wells by: (a) possibly utilizing the gravel as a gas trap in pumping gaseous fluids, (b) allowing deep submergence of the pump into the oil zone. In a conventional well—that is, where the liner is set in an open hole-. even though perforation sizes are chosen according to known rules based on analysis of sand grains from samples from the zone, there is likely to be some production of sand. This may be due to the miscalculation of

Jan 1, 1940

By Freeman Bishop

President Allende says he will expropriate all American investments in Chile and he's already well on the way to accomplishing this objective. What the average observer doesn't realize is that this has not only created big lossess for the copper companies. It could also take a chunk out of the U.S. taxpayers' pockets. Premier Castro expropriated the U.S. taxpayers' investment of over $100 million in the Nicaro (Cuba) nickel and cobalt operations-and U.S. Government protest over the loss was never heard above a whisper. Where the taxpayer comes in today is through the Overseas Private Investment Corporation, which was set up to guarantee U.S. companies' foreign investments against losses due to political changes. As of now, metals firms hold more than $300 million worth of obligations against this U.S. Government agency. The agency itself may not be able to raise more than $85 million, and a supplemental appropriation may be needed to meet its guarantees.

Jan 1, 1971

By Marshall D. Himes

The Pima mine, Pima County, Ariz., a 53,500-tpd copper mine, is located 17 miles south of Tucson, Ariz. The mine is in a sequence of Paleozoic and Mesozoic sediments striking east-north-east and dipping southeasterly. These sediments are intruded by a Tertiary quartz monzonite porphyry. The Paleozoic Permian (?) dolomites, limestones, and sandstones have been altered to calc-silicate skarn, marble, and quartzite. The overlying Mesozoic Triassic (?) clastic sediments have undergone some recrystallization and hydrothermal alteration. The clastic metasediments are divided into three distinct lithologic units: lithic arenite, arkose, and interbedded and overlying black argillite. Three types of hydrothermal alteration in the clastic rocks are propylitic alteration (epidote, chlorite, and quartz, with or without sericite), quartz-sericite alteration, and potassic alteration (K-feldspar, quartz, and sericite, with or without chlorite and calcite). The porphyry has undergone potassic alteration. Dominant structures are an east-west postmineral fault in the western part of the pit, and strong low angle faulting and shearing which truncates the ore body at depth. The two joint sets, one parallel to bedding and the other at right angles to bedding are prominent in the mine. Faulting is in two dominant directions, one striking northwest, dipping northeast, and the other striking northeast, dipping northwest. Economic mineralization is prediminantly disseminated pyrite and chalcopyrite, and molybdenite-quartz veinlets. There are less important amounts of magnetite, hematite, sphalerite, galena, tennantite, and bornite. Mineralization is believed to be both structurally and chemically controlled.

Jan 1, 1974

By Theo W. Robinson

The evolution of the modern blast-furnace from the embryonic stages of comparatively few years ago, has been the work of wide praetiee and experiment. That much is still to be desired, the experience of every furnace-manager mill testify. Mr. Walsh's paper on "The Irregularities of the Blast-Furnace Process, and a Practical Way to Avoid Them" (Trans., xv., 419), proposes a new solution of the problem of interior lines, and one that has given rise to not a little speculation and controversy. The investigation described in this paper was undertaken to test experimentally the theory of Mr. Walsh as to maximum reducing capacity. Briefly explained, Mr. Walsh's views (outside of his claim for increased efficiency due to having the bosh wholly within the meltingzone) are, that a furnace of contracted stack and throat, on his lines. may equal in product one of considerably greater cubical capacity. The explanation offered for the theoretical greater capacity per cubic foot of his furnace is, that the increased tension of gases caused by passing through the small area mill promote transpiration, thus facilitating reduction and permitting more rapid driving. This alleged relation will appear from a hypothetical case in which a furnace, A, constructed on Mr. Walsh's lines, has but 1/x of the cubical contents of a furnace, B, of modern type; the two being equal in height. In order that A shall have the same capacity as B, both working normally with the same mixture and burden, and

Jan 1, 1889

By John H. Melvin

THE Omaha District, Corps of Engineers, has been doing subsurface exploration work for a number of years, both by contract and with its own forces. Certain practices and procedures concerning the recovery of large diameter cores have been developed which will be described in this paper. GEOLOGY Most of the drilling to date has been in connection with structures on the main stem of the Missouri River above Sioux City, Iowa. A wide variety of subsurface conditions has been encountered. The bedrock formations appear in regular order from the oldest to the youngest, traveling upstream; or in other words, the general regional dip is to the northwest. The oldest formation is the Carlile shale, a compaction or noncemented waxy shale of Cretaceous age. Because of its uncemented, soft nature this shale has a tendency to grind or wash away when drilled. It also has a tendency to rebound or expand when the overlying pressures are removed. A 25-ft bed of sharp, friable sandstone called the Codell member is present near the top of the Carlile shale. This member is a cemented sediment, but in drilling, many of the sand grains are broken loose and exert extensive abrasive action on the core barrel and bit. Above the Carlile shale is the Niobrara chalk, a soft calcareous deposit with shaly horizons and some thin beds of bentonitic clay. The average thickness of this deposit is about 145 ft. It is soft enough to be sawed or bored with ordinary woodworking tools, yet is compact enough to be used as building block. The Pierre shale, the formation above the Niobrara chalk, is over 800 ft in thickness and is the most widespread material in the area. It is a dark colored, compaction shale containing numerous thin bentonitic clay seams and at certain horizons, hard manganese concretions. The shale has numerous faults and in addition, along the valley walls, has undergone considerable - slumping. Joints, fault planes and slickensided surfaces are common features encountered in drilling and add to the difficulties of high core recovery. East of the Missouri River the bedrock is generally covered with from 100 to 200 ft of glacial till, composed of clays, silts, sands, gravels and boulders. The valley itself is filled with alluvial deposits, mostly of the sand and gravel sizes, and contains a buried preglacial or interglacial channel over 100 ft in depth. The overburden deposits require sampling in connection with engineering studies and must also be cased before the underlying bedrock can be cored. The diameter of the required overburden samples can thus have an indirect effect on the size of core recovered from the bedrock. West of the river, which in most cases is the western boundary of glaciation,

Jan 1, 1947

By Arthur Hockman, Howard W. Jaffe, Howard F. Carl

THE problem of establishing practical techniques for evaluating natural corundum ores arose from the desire to improve the existing purchase specifications for crystal corundum procured by the Federal Government for stockpiling. Such purchase specifications had been developed for a large number of products, including minerals and ores considered to be critical and strategic because of the country's dependence on foreign sources of supply. It will be apparent to anyone considering the subject of purchase specifications that the determination of whether or not a submittal meets the specifications is a prime consideration. Consequently satisfactory specifications for minerals should not only incorporate physical, chemical, and mineralogical requirements that are practical but should also establish the means by which both buyer and seller can be assured that materials meet stated requirements. The Munition Board's Material Purchase Specification for corundum, dated February 1954, covered two grades of crystal corundum intended primarily for abrasive use. It established limits of size and of composition: Grade A, at least 95 pct +3 mesh and 92 pct alumina (Al2O3); Grade B, at least 95 pct +7 mesh and 90 pct alumina. It also specified that "of each lot of material, not less than 95 percent shall have a hardness equal to or exceeding nine (9) on Moh's Scale." These specifications were unsatisfactory for several reasons. They did not allow the purchase of lower grades of corundum being used by industry. Neither did they specify exactly what a corundum ore actually was, except that it should contain so much alumina and have a certain scratch hardness. Nothing was said about the abrasive qualities of the material that was to be purchased primarily for abrasive use. During the period 1946 to 1948 supplies of the two grades defined in the then current specifications continued to decrease. Early in 1949 industry recommended that the finer sizes of corundum known as "crystal corundum concentrates," ¼-in. to 16-mesh material, be added to the stockpile specifications and that lower grades of crystal corundum also be included. In the spring of 1949 the National Bureau of Standards and the Bureau of Mines were asked by the Munitions Board to cooperate in developing more practical specifications for grading natural corundum ores. The National Bureau of Standards indicated that it would investigate physical test methods for determining abrasive characteristics of corundum, and the Eastern Experiment Station of the Bureau of Mines at College Park, Md., stated that it would consider the mineralogical aspects of the problem. Members of these two agencies, in consultation with representatives of the Office of Materials Resources of the Munitions Board and of the Federal Supply Service of the General Services Administration, and with the cooperation of industrial suppliers and consumers of abrasive corundum, developed, in a fairly short time, more practical specifications for six grades of corundum ores. The new specifications, issued January 1951, were for corundum, natural crystals, as by this time high-purity synthetic corundum was available and widely used. Nevertheless, for certain specific applications the natural product was preferred over the synthetic material. It has been extensively used in forming snagging wheels. It breaks into more or less cubical particles, whereas artificial corundum fractures into splintery shapes. These produce irregular cuts in glass, while the more symmetrical shape produces a more uniform ground surface. For this reason natural corundum has been preferred for certain types of lens grinding. Pure corundum is clear, colorless alpha alumina (A12O3), but it is rarely found in nature in this form. The most important gem varieties include the blue and yellow sapphires and the ruby. Minute impurities of titanic oxide impart a blue color,

Jan 1, 1955

ONE of the fundamental reasons for the extreme rapidity with which the Porphyries developed after the trail had been blazed at Bingham was the amenability of the deposits to prospecting and proving of the ore either by churn-drilling or by diamond-drilling. At Ray churn-drill data formed the principal basis for early calculations of ore reserves; and in 1913, Inspiration floated its first bond issue for $6,000,000 on the strength of the estimate of 45,000,000 tons of sulphide ore assaying just over 3 per cent copper. The money was obtained in spite of the fact that no one ever had actually laid eyes on more than a minute fraction of that ore. The customary method of developing a copper deposit before the Porphyry era had been to sink shafts or drive adits and then to follow and expose the veins or lodes with horizontal and vertical underground workings-drifts, crosscuts, raises, and winzes. The excavated material sometimes was sampled in bulk; but always the walls of the openings would be channeled at intervals to obtain small samples representative of the ore left in place. This process was known as "blocking out" ore. It was costly and it required a great deal of time to prove the existence of immense tonnages. The early development at Utah was done in this way; likewise, at Miami. This fact helps to explain why only 3,000,000 tons of ore was reported as being developed when J. Parke Channing wrote the report on which the original Miami financing was based in March, 1908. Fortunately, his 3,000,000 tons averaged 3'per cent copper. At Ray, Seeley W. Mudd estimated 3,000,000 tons of ore in June, 1908, developed principally by underground working; but by the end of 1909, Henry Krumb was able to report 50,000,000 tons as the fruit of a little more than a year of churn-drilling.

Jan 1, 1933

By William E. Ford, Edward Salisbury Dana

The monoclinic Wolframite Group and the tetragonal Scheelite Group are included here. Wolframite Group WoIframite (Fe,Mn)W04 a : b : c = 0.8300 : 1 : 0.8678 B = 89' 22' Hiibnerite MnW04 048362 : 1 : 0.8668 89' 73' WOLFRAMITE. Monoclinic. Axes a : b : c = 0.8300 : 1 : 0.8678; B = 89' 22'. mm"', 110 A 1TO = 79" 23'. ay', 100 A 101 = 62' 54' at, 100 A 102 = 61" 54'. $', 011 A 011 = 81" 54'. Twins: (1) tw. axis c with a (100) as comp.-face; (2) tw. pl. k (023), Fig. 449, p. 171. Crystals commonly tabular (1 a (100); also prismatic. Faces in prismatic zone vertically striated. Often bladed, lamellar, coarse divergent columnar, granular. Cleavage: b (010) very perfect; also parting (1 a (100), and 11 t (102). Fract,ure uneven. Brittle. H. = 5-5.5. G. = 7.2-7.5. Luster submetallic. Color dark

Jan 1, 1922

By R. Pakalnis, J. P. Savely, R. D. Call

A simple and inexpensive clay imprint core orienting device has been developed by Dr. R. D. Call. It has a minimum of moving parts, is durable and easily used by drillers, and adds only 15 minutes to a core run. Conventional wire-line drilling and a drill hole inclined 30° to 60° from the horizontal plane are required. The device will not operate in a vertical hole. The orientor is an eccentrically weighted downhole device which can be constructed in a mine shop from an old inner core barrel and lead. Modeling clay is packed in the core lifter case, which is screwed on the downhole end of the orientor. A clay imprint of the bottom of the hole is taken after each coring run. This imprint is matched to the top of the succeeding core run, the drill core is pieced together, and a reference line representing the drill hole is scribed on each core. Fracture attitudes are measured relative to the reference line and the core axis. On recent drilling projects, tests for imprint reproducibility were conducted. The results of these tests show an average variation of f3" in location of the scribed reference line between imprints. Comparisons of surface mapping data with oriented core data are good. It is rare that the entire length of drill core in intensely fractured zones can be oriented because it is impossible to piece the core together. However, if a triple tube set-up is used, a modification in the scribing procedure can result in a good statistical sampling of the fracture population. Attitudes of major structures have been oriented with this technique.

Jan 1, 1983

By George C. Ference

Sulfur is the 13th most common element in the earth's crust, constituting approximately 0.05% of the total. It occurs naturally in its elemental form, as metallic sulfides, nonmetallic sulfates, and as combined or free sulfur in natural gas, crude oil, and coal. COMMERCIAL SOURCES Most of the sulfur that is consumed is converted into sulfuric acid before use; therefore, it is not necessary to recover sulfur solely in its elemental form. Processes for recovery are peculiar- to the types of reserves being processed. The major commercial processes as well as the general geographic locations where the appropriate reserves occur are listed in the following. It should be noted that the sulfur values may be recovered as the primary product, as a coproduct with other materials, or as a byproduct. Elemental Sulfur 1) Frasch mining is used for subterranean deposits of elemental sulfur around the Gulf Coast areas of the United States and Mexico. Generally, but not exclusively, such deposits are located in salt dome structure. 2) Autoclaving, flotation, or solvent extraction of surface deposits of elemental sulfur is practiced throughout the world. 3) Extraction and conversion of hydrogen sulfide from sour natural gas into elemental sulfur is done principally in Canada, France, and the United States. 4) Conversion of metallic sulfides from pyrites into elemental sulfur is done via the Outokumpu process in Finland. 5) Catalytic cracking and hydrocracking of sulfur-bearing crude oils to produce elemental sulfur is done worldwide. Desulfurization of refined petroleum products also yields elemental sulfur. 6) Recovery of elemental sulfur from sulfur-bearing oil sands (Athabasca tar sands) has been initiated in Canada. 7) As of this writing (1970), a plant has been constructed for the thermal decomposition of gypsum to produce elemental sulfur in the United States. Sulfuric Acid Sulfur values in the form of sulfuric acid are recovered via: 1) Recovery from smelter gases throughout the world. 2) Roasting of pyrites throughout the world with iron sinters as a byproduct. 3) Roasting of anhydrite with cement as a coproduct, primarily in Europe. 4) Processes currently are being developed for recovery of sulfuric acid from combustion gases resulting from the burning of high-sulfur-content fuel. Other Sulfur values also are recovered from waste products which normally occur in highly industrialized areas. Some examples are: coke-oven gases, sludge sulfuric acid, and pickling liquors (ferrous sulfate).

Jan 1, 1976

By Donald L. Johnson

REVIEWS on the applications of optical ellipsometry to the study of polycrystalline metal surfaces and oxidation-corrosion processes have been presented by Kruger and Hayfield, and white.' In view of the ability of this method to measure differences in film thicknesses to below 10A, ellipsometry was used to study nitrogen chromium surface reactions during the early stages of growth. Chromium specimens in the form of a vapor-deposited film on glass substrate were exposed to purified nitrogen for selected time increments at 700°F. This temperature was selected because it gave the best combination of exposure time and thickness change. Ellipsometer readings were taken immediately after exposure to determine polarizer and analyzer angles using monochromatic light at 5000A.2 After each set of readings was obtained, the specimens were exposed for an additional increment of time in nitrogen and a new set of readings taken. Film thickness was computed from LUCy's3 equation for nonabsorbing thin films. In Lucy's derivation, two equations for computing thickness were obtained. Peterson and Bashara4 have discussed the validity for using one of these equations when an independent value of the refractive index is used. The film was assumed to be Cr2N (Ref. 5) and was determined to be optically isotropic. Optical isotropy was determined by rotating the films about the surface normal and noting that the azimuth and phase difference did not change. Since Cr2N is reported to be hexagonal, it is assumed that optical isotropy results from randomly oriented grains of very small size. The thickness was computed using refractive indexes varying from 1.6 to 2.0. The maximum variation in computed thickness over this range for a given exposure was 20 pct. The data reported are based on a refractive index of 1.8. Reference readings on the metal surface were taken just prior to nitrogen exposure. No attempt was made to deoxidize or denitride the metal surface after vapor deposition, although specimens were observed to gain approximately 2A per day in air at room temperature. Twelve experimental exposures were made on a single sample over a total accumulative time of 132 min. Additional experiments over longer time intervals were made to determine the effect of heat up and cool down during and after exposure. As a result of these experiments, the thickness computed for each exposure was increased by 4A. Time profiles based on the linear law are similar to the oxidation profiles for many metals.' The rate of accumulation of the nitride film is rapid at first and slows down as the film thickness increases. The parabolic law x2 =k1t +k2 [11 gives a straight line in Fig. 1; therefore, it is concluded that the kinetic behavior is parabolic. Sey-bolt and Haman5 reported similar results for CrlN on chromium at 1000°C although the order of the thickness was much greater (10-3 cm). Analysis of thickness data based on other values of refractive index shows that the curves are shifted vertically but retain the same shape. According to Mott,7 it is expected that for thin films k2 is zero in Eq. [I]. Since the plot in Fig. 1 is linear through the origin, k2 is zero and the parabolic nature of the film growth is further indicated. The parabolic rate constant, calculated from the slope in Fig. 1, is 4.4 x 10-16 sq cm per sec. The corresponding work (+) required to bring an electron from the metal into the oxide is estimated to be 1.5 ev.7 The author thanks professor N. M. Bashara and D. W. Peterson, Electrical Materials Laboratory, University of Nebraska, for making the ellipsometer available and providing technical assistance. The Electrical Materials Laboratory is supported by the office of Naval Research, NONR 3718 (01). This work was partially supported by the Engineering Experiment Station and the Mechanical Engineering Department, University of Nebraska.

Jan 1, 1967

By M. I. Sherman, J. D. H. Strickland

PRELIMINARY experiments in these laboratories showed that whereas pyrite1 produced only sul-fate the action of aqueous chlorine solutions on most other sulfide ores resulted in the formation of a mixture of sulfate and elemental sulfur, the production of the latter being favored by a very dilute solution of oxidant. The reactions taking place were obviously complex and only a detailed kinetic study could be expected to clarify the position and enable a prediction to be made of conditions leading to the rapid formation of metal salt and the economically desirable elemental form of sulfur. Galena was chosen for the first investigation as it is of widespread occurrence and is representative of a simple cubic lattice sulfide containing the monosulfide unit, S2-. Experimental Procedure The apparatus and general technique used in this work have already been described.' Analyses for chlorine and sulfate were carried out by the same methods as those used for pyrite. The lead in 1 ml aliquots of solution was determined polarographi-cally, after destroying chlorine with hydrazine hy-drochloride and making solutions 0.5 molar with hydrochloric acid. A large sample of Kansas galena, assaying at better than 98 pet PbS, was crushed and wet sieved to give fractions of —10 + 14, —20 + 28, —28 + 35, and —48 + 65 Tyler screen. The particles were almost perfect cubes and the apparent surface Per gram was calculated assuming each particle a cube Of side equal to the mean mesh opening. A volume shape factor, calculated as for pyrite, was exactly unity. The main apparatus was unsuitable for direct visual examination of the ore particles during the reaction. For this purpose a small cell from a Spekker Absorptiometer optical flats 1 cm apart) was l by a greased microscope slide after filling with oxidant solution. One or two ore particles were placed in the cell and the solution was stirred by a glass covered speck of iron wire activated by an external rotating magnet. The surface of an ore particle was examined under a binocular microscope at between 10 and 40 magnifications. Results Experiments were made under a wide variety of conditions, the form of presentation of the data being illustrated by Fig. 1, where the concentrations of chlorine, sulfate, and sulfur are plotted against time. The fictitious concentration of solid sulfur is used for convenience and is the molarity of sulfur which would be recorded if the elementary sulfur formed during the reaction were dissolved in the liquid iii the reaction vessel. As some lead sulfate is occluded with the sulfur on the ore particles the amounts of sulfur and sulfate formed during a reaction cannot be calculated

Jan 1, 1958

By C. W. Bildt

During many years of service in the iron and steel industry I have frequently found, as have also many other engineers, that the common devices used for feeding coal into gas-producers are not what they ought to be in order to secure the best economy. The hopper-and-cone so generally used is familiar to all, and a brief study of its action will surely satisfy everybody that this device has several serious faults. In the first place, the charging is intermittent, and depends entirely upon an attendant. When the hopper is frequently emptied, it may work fairly well, but even then it suddeinly discharges into the hot producers a large body of coal, which is often violently converted into gas that rushes into the furnace, and, as the damper for the combustion-air cannot be regulated every time the producer is charged, there will be an excess of gas, which goes up the chimney unburned. Between the chargings the quantity of gas generated decreases, and there will often be an excess of air in the furnace,

Jan 1, 1899

By Carl Tolman, LeRoy Scharon, Harold Powers

THIS paper presents geophysical and subsurface data observed in the vicinity of Shafts No. 1 and and 5 of the National Lead Co. lead mines at Fred-ericktown, Madison County, Missouri, see Fig. 1. The area selected is an excellent example to illustrate the close correlation between geophysical data and geological facts as revealed by drilling and mining. Such close correlations make geophysical applications appropriate to the development of known ore-bodies as well as the exploration for new orebodies. In the past, magnetic and shallow electrical resistivity observations were made over limited areas in the Fredericktown lead district by the Missouri Geological Survey, with favorable results. The first extensive magnetic and electrical resistivity surveys were started by the U. S. Bureau of Mines in May 1945 in two areas located northwest and southwest of Fredericktown, as shown in Fig. 1. The results of these surveys were reported in April 1948 at Denver, spontaneous-polarization surveys were made over the property of the St. Louis Smelting and Refining Co. at Fredericktown by Sherwin F. Kelly Geophysical Services, Inc. Aeromagnetic surveys were completed in 1948 over the Fredericktown quadrangle by the U. S. Geological Survey. Since 1945 geophysical surveys have been an important part of exploration programs in the Fred- ericktown district. Such methods, magnetic and electrical resistivity, are now serving as guides in the further development of known orebodies. On an irregular pre-Cambrian igneous erosion surface Lamotte sandstone of upper Cambrian age was deposited, partially filling the topographic basins, see Fig. 2. Above and conformable with the Lamotte sandstone lies the Bonneterre formation, a dolomite with locally interbedded thin dolomitic limestones and shales at its base. This formation also only partially filled the topographic basins. The Bonneterre was overlain by the Davis, Derby, Doe Run, and Potosi formations, which are principally dolomite. Uplift, tilt, and slight warping has allowed erosion and weathering to remove most of the sediments overlying the Bonneterre, and in many places, not far from the mine, the Lamotte sandstone is exposed. This erosion has also exposed areas of pre-Cambrian igneous rock. The Lamotte sandstone, having been deposited on an irregular pre-Cambrian surface, is extremely variable in thickness and ranges from zero where it laps the pre-Cambrian rocks to 250 ft thick in the deeper basins. In the vicinity of the mines the Bonneterre dolomite ranges from zero where it wedges out against the pre-Cambrian igneous rocks to 400 ft thick. The ore deposits occur as a bedded disseminated type1 and are chiefly composed of galena and pyrite with minor amounts of chalcopyrite and siegenite. Heavy pyrite and marcasite mineralization may be found throughout the Bonneterre formation. However, there is little or no apparent association of these iron sulphide bodies lying above the ore hori-

Jan 1, 1954