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By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By H. C. Miller

THE gas-lift method of flowing oil from wells is the outstanding feature of petroleum technology today. Its forerunner, the air lift, was used successfully first, in the Baku fields of Russia, in 1899, and later in the Gulf Coast fields of Texas and Louisiana and the Kern River field of California. It is still used to a limited extent in certain oil fields. The use of compressed natural gas for lifting oil from wells has supplanted the air-lift method in a measure in those fields where a sufficient quantity of gas accompanies the oil to make the gas lift possible, or where natural gas is plentiful and inexpensive. We find therefore in California, that, natural gas is used at practically every well where a gaseous medium is employed to flow the oil. The use of natural gas has many advantages over that of air. It is possible to recover and save the gasoline from the gas that accompanied the oil to the surface. This gasoline would be wasted if air were used as the lifting medium. Also, certain proportions of air and gas form an explosive mixture that cannot be handled safely by compressors. Another advantage that gas has over air is that gas under pressure is more soluble in oil. Gas in solution in oil reduces the viscosity of the oil that is being produced and causes it to flow more readily through the. tubing and flow lines. The gas lift has made it possible to recover many thousands of barrels of oil from deep wells in California that could not have been produced otherwise. It would not have been economical, had it been mechanically possible to produce such wells as the world's deepest producing oil well (Miley Athen's No. 6, Rosecranz field, California) by any other method of pumping known today. At this well, production is obtained from between 7305 and 7591 ft. and 11 months after completion of the well, production was being maintained on the gas lift it approximately 2000 bbl. a month. The crookedness of the hole, or its diameter and depth will not prevent the successful application of gas-lift pumping when other conditions are favorable.

Jan 1, 1927

By Behram H. Wadia, Robert S. Lehto

A new metallurgical treatment for capturing as much of the values as possible from zinc refinery feed has been devised by personnel in Cerro de Pasco's Peruvian operation at La Oroya. Results from a pilot test illustrate that 50 metric tons of throughput can be maintained whereby substantially all the silver and copper report in the sponge iron while zinc and lead with indium and cadmium volatilize in the fume. This new technique named the Zileret (zinc leach residue treatment) process complements the electrolytic system used in the refinery so that all values in a zinc concentrate are economically recovered. In the system, dried zinc leach residue is pelletized with soluble zinc sulfate which already exists in the leach residue and a finely divided reducing agent such as anthracite coal. Upon heat addition, the loose anthracite in the charge maintains a reducing atmosphere while the free space above the charge has an oxidizing nature. When the charge reaches the reaction zone at about 1100°C, metals such as zinc, lead, cadmium and indium volatilize from the pellets, are oxidized in the upper kiln atmosphere, and are then carried in suspension as an oxide fume to the cooler and baghouse. The copper and silver content in their reduced forms, along with the iron, discharge from the kiln as a calcined product which is then cooled to below 130°C before being exposed to the air.

Jan 9, 1969

By T. S. Spice, H. L. Lovell, R. W. Utley

With the increased demand for lightweight aggregate, such materials have been manufactured from slags, clays, slates and, to a minor extent, the refuse of coal preparation processes. The latter source is attractive due to current interest in eliminating air pollution and improving the unsightly appearance of refuse piles as well as potential economic advantages, if a satisfactory product can be manufactured. A study has been made relating the composition of coal refuse, expressed as washability data, and the properties of a resulting aggregate. Three different refuse samples (bituminous and anthracite) were separated at gravities ranging from 1.4 to 2.96. Their chemical composition was determined. Aggregates were prepared in the laboratory from these fractions before and after ashing, at temperatures between 1250' and 1350°C. The specific gravity, expansion and compressive strength of the products were measured. The response of the refuse to bloat is related to the chemical composition of the ash to yield a glass of desirable viscosity and to the presence of a material which will form a gas in the appropriate temperature range. Carbonaceous material within the particle is a negative factor since after the glassy phase forms, oxygen cannot enter the mass thus inhibiting bloating. Precombustion of the refuse is also detrimental since it removes substances of gas-forming capability. The fraction sinking at 2.60 yielded an aggregate which had the lowest specific gravity, greatest expansion and greatest compressive strength. The purpose of this study was to seek and evaluate possible relationships between the composition of coal refuse, as expressed by washability data and factors affecting the production of a lightweight aggregate from refuse by bloating. The study was related to an intense program in the Department of Mineral Preparation at the Pennsyl- vania State University to study the possible elimination of air pollution from coal refuse fires by producing a low-carbon secondary refuse. Another phase of this program is considering possible uses of such a secondary refuse. Thus one study was to determine if a lightweight aggregate could be produced from this new refuse material and what effect the nature of refuse beneficiation would have upon the characteristics of a commercial aggregate product. It was hoped that these studies would assist in the design of a process and in establishing the optimum specific gravities at which refuse separation could be made in respect to the production of a low grade fuel from the float product and a raw material for lightweight aggregate from the sink product. The combination of producing a saleable low grade fuel and a lightweight aggregate, while at the same time minimizing disposal costs and air pollution contributions would be attractive to the coal mining industry. MECHANISM OF BLOATING Austin, Nunes and Sullivan,1 Ehlers,3 Everhart, 4 Riley7 and others, have stated that bloating is an expansion process in which two essential conditions exist simultaneously. These are: the development of a glassy phase over a relatively wide temperature range (the viscosity of this glassy phase plays a major role in the retention of the evolved gases) and the evolution of gases (SO2, SO3, CO2 and O2) from mineral decomposition in sufficient quantities at appropriate temperatures to form a cellular structure in the mass. Unless these two "type" reactions take place at the same time or in overlapping ranges of time and temperature, cellulation will not occur. In this event, the gas will escape or the melt will be too fluid to retain it; or if retained, the cells may be too large or the walls too thin for good strength in the product. The stages that occur when clays and shales are heated in an oxidizing atmosphere may be summarized as follows: 1) Drying and removal of free water to 200°C. 2) Absorbed water dehydration period (200 to 480°C). 3) Chemically-combined water dehydration period (480 to 700°C).

Jan 1, 1965

By N. V. Hansell

The last few years have shown an increasing interest in the subject of beneficiating iron-ores in all iron-producing countries. In the United States, this movement has been slower than in certain parts of Europe, for the obvious reason that the abundance and relative cheapness of the Lake Superior irou-ores has hindered the development of enterprises for the preparation of low-grade ores. Gradually, however, conditions have changed. The world's consumption of iron is increasing enormously. Being in 1900 about 40,000,000 tons, in 1910 it was already 60,000,000; and there is no reason to doubt that for the near future the increase in iron-cousumption mill continue at the same rapid rate, especially with the development of China, certain parts of Africa, and other regions which have hardly been touched as yet by modern industrialism. It is, therefore, not surprising that apprehension is felt that the known available iron-ore resources of the world are gradually being depleted. Signs of this feeling are the recent iuvestigation, under the direction of the U. S. Geological Survey, of the iron-ore resources of the United States, and the estimate presented to the last International Geological Congress, at Stockholm, Sweden, of the iron-ore resources of the world. These investigations have emphasized the fact that the known high-grade ore-deposits are limited in extent, and will, at a not distant future, be exhausted, compelling the iron industry to depend for raw material on the enormous deposits of low-gratle ores which are distributed over almost all the world. The discovery of new deposits of high-grade ore, in countries not yet thoroughly explored, will not materially change this prospect. Of course, the part which such new deposits will play in the future cannot be forecast. The difficulty and cost of transportation will probably exclude many of them from use at the present centers of the iron industry.

Jan 1, 1913

By C. G. Dunn

This note describes a method for revealing micro-structures in tantalum through an {hkl} effect which was found during a study involving amorphous and crystalline tantalum oxides. Three steps are involved. First, an amorphous film of Ta2O5 is formed anodically1 on the surfaces of the tantalum. The amount needed depents on the thickness of the substrate tantalum; 1600Å of oxide, however, is generally satisfactory in the 1/2 -mil (12 µ) to 3-mil thickness range. The film at this point is uniform in color. Second, the anodized specimen is heated to 800°C in. vacuo during a period of a few minutes and held at temperature for 5 min. During such a treatment some oxygen leaves the oxide through dissolution into the substrate tantalum (e.g., at 10-8 Torr oxide films thinner than about 800 completely disappear on 5-mil strip). Considerable crystallization of the amorphous oxide also occurs adjacent to the metal/oxide interface but not throughout the oxide thickness. The thickness of oxide needed as a residue is not too critical; values between 500 and 1000Å (optical estimate') may be most useful. (The presence of a residual oxide layer after the heat treatment usually is not apparent; in fact, in most instances the surfaces have a metallic appearance. This can be the case also for thicker residual films needed in the detection of a crystalline oxide phase by surface X-ray diffraction—e.g., if the initial oxide film is 3000Å thick, enough crystalline oxide is formed for X-ray detection.) The third step eliminates the metallic appearance at the surface and reveals (or produces) a varied colored film of tantalum oxide. Two methods can be used and both will be illustrated. If the specimen is dipped in 48 pct HF for a few seconds, the tantalum is found to be covered with a multicolored oxide. Moreover the colors correlate with the grain structure of the substrate tantalum through an orientation dependence of the type illustrated in Fig. 1, where results of an orientation analysis by the Laue X-ray method have been plotted. Other film conditions would have provided a different set of colors for the same orientations. Any such correlation, however, provides a basis for a qualitative assessment of the distribution of orientations in a large sample. The cold-rolled structure of tantalum foil produced by a recrystallization anneal and a cold-rolling reduction of 95 pct is not easily obtained by usual metal-lographic methods.' The structure, however, is easily revealed by the present technique, Fig. 2. The alternative third step is to reanodize the specimen. The optical nature of the final anodic film depends on the presence of the crystalline oxide phase; color variations indicate optical thickness variations in the film. As the reanodization voltage is increased from zero, straw and light brown colors appear (as usual), followed now by variations in color from grain to grain depending on {hkl} orientation. Suitable end points, which are determined by voltage and time, are easily established. Fig. 3, for example, shows the grain structure developed in 5-mil tantalum strip during a 30-min re-crystallization and grap-growth anneal at 1800°C. An anodic film of 1600Å thickness was added prior to the special 800°C anneal. Reanodization was done at constant current density (near 0.2 ma per sq cm) in an aqueous solution of H3PO4 (0.01 pct) and was terminated after the initial brown colors were replaced by a deep blue at approximately 30 v. Although good grain contrast can be obtained with bright field illumination, even greater contrast for black and white micrographs may be obtained with polarized light, as in Fig. 3.

Jan 1, 1967

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who registered at Institute headquarters during the period Mar. 10 to Apr. 10, 1915: Oscar Lachmund, Greenwood, B. C. Harvey B. Small, Mangaugue, Colombia. S. W. Ough, Pachuca, Mexico. M. F. Sayre, Schenectady, N. Y. B. W. Vallat, Detroit, Mich. James W. Hambleton, Parral, Mexico. Charles Mentzel, New York, N. I . Philip L. Gill, Woodmere, L. I., N. 1. M. K. Rodgers, San Francisco, Cal. John T. Fuller is President of the F. Shepherd Mining Co., operating at Rush Mountain, Ark.

Jan 5, 1915

By L. Yarborough, L. R. Smith

This paper presents results of a laboratory study of retrograde condensate recovery by revaporization into dry injection gas. Flow tests were performed in 10.6-ft long sand packs at 100F and 1,500 psi. In three runs methane revaporized the liquid from a n-pentane-methane mixture in the presence of immobile water. TWO of these tests were water-wet, and the third was totally oil-wet. In the three runs n-pentane recovery was complete after 2.5 hydrocarbon PV of injection. There was no significant performance difference between the two wettability extremes. In a fourth experiment, a methane-hydrogen sulfide mixture revaporized a synthetic light, sour condensate. No water saturation was present. Equilibrium compositions and volumetric data were obtained for the four-component condensate. The heavy component, n-beptane, was removed after 6 PV production. Comparison of the effluent fluid compositions with known equilibrium data shows that the flowing fluid was equilibrium vapor and that the mixing zone between equilibrium vapor and dry injection gas was short. Data indicated that complete recovery of retrograde liquid occurred after it was contacted by a sufficient quantity of dry gas. INTRODUCTION When pressure declines below the fluid dew point in a gas condensate reservoir, a liquid phase forms. In this process, referred to as retrograde condensation, the quantity of liquid formed is frequently small enough that the liquid is not a flowing phase. To prevent loss of valuable retrograde liquids, the process of dry gas cycling has been employed for several years as a more or less standard practice. In this procedure the reservoir pressure is maintained above the fluid dew point so that the liquid components may be produced as vapor and then separated at the surface. Although full pressure maintenance by gas cycling seems ideal in terms of preventing liquids loss, several factors can reduce the atuactiveness of such an operation. From a study of a condensate reservoir in Alberta, Canada, Havlena et a1.1 con-cluded that cycling under conditions of declining pressure leads to economic advantages and to a high recovery of hydrocarbon liquids. This study considered effects of volumetric sweep efficiency, retrograde behavior of the original wet gas and revaporization characteristics of the retrograde liquid when contacted by dry gas. The first major work concerning revaporization of liquid in a gas condensate system is that of Standing et a1.2 Calculations based upon the PVT behavior of a recombined gas condensate fluid indicated that all retrograde liquid can be recovered if it is contacted by a sufficient quantity of dry gas. The paper considered the effect of variable permeability upon the recovery of retrograde liquid. Standing et al. concluded that recovery of heavier components in the retrograde liquid is greatest if reservoir pressure is allowed to decline below the dew point prior to dry gas injection. Since the work of Standing et al., several laboratory studies have been reported which show that recovery of hydrocarbon liquids by vaporization into dry injected gas can contribute to increased recovery above that obtained by ordinary production practices. Vaporization from retrograde condensate,3 conventional oil4-7 and volatile oil8 reservoirs has been considered. There is little work that deals with revaporization recovery from condensate reservoirs. This study demonstrates that vapor-liquid equilibrium exists when a dry gas is injected into a porous medium containing retrograde condensate; investigates the effect of wettability on revaporization of retrograde condensate; and provides an indication of the amount of dry gas necessary to

Jan 1, 1969

By B. Ramaswami, U. F. Kocks, B. Chalmers

This paper describes the tempetrature, solute (gold), and orientalion dependence of the plastic rleforlirnlion of silver single crystals. The virgin flow stress, To, and its temperatutre dependence incrense with increase in solute concentration. el decreases with decrease in temperature below room teiirperature and with increase in solute coucentralion. The dependence of 011 on temperature arid solute sontenl is due to the dependence of Ts on the two variables. An increase in ts, due to either the temperature or the solute conlent, results in a decrease of e11 in crystals of single-slip orientation and an increase of 011 in crystals of' (100) find (111) orientation. is orientation-dependent and at all the temperatures and in all the materials studied. The Leveling off of the engineering stress-strain curve in crystals of (100) 07-ientotion at a stress tl, is associated with extensive cross slib. The temperature and strain -rate dependence of tl are similar to those of indicating that a rate process is the cause 01 this phenomenon. The plastic deformation of silrer crystals of (110) orientation is multiple to that of crystals of single-slip orientation. THE work hardening of fcc crystals has been the subject of intensive investigations in the past 15 years. The effect of orientation, deformation temperature, solutes, second phase or precipitates, strain rate, etc., has been studied in a number of fcc metals.'-5 In spite of the considerable amount of work reported on the dependence of work hardening on the orientation, temperature, and solute concentration, certain aspects of the plastic deformation of fcc crystals have not been clarified. For instance, with the exception of a few investigations,6-8 where crystals of multiple-slip orientations have been studied, almost all the studies have been on crystals of single-slip orientations. Hence, a major portion of this study has been devoted to the dependence of plastic deformation on the multiplicity of slip systems and the enhanced possibility of dislocation interactions resulting from such multiplicity. Further, the abnormally low rate of work hardening observed at large strains at certain temperatures in crystals of the (100) orienta-tion 6-8has not been explained satisfactorily. It is the aim of this study to clarify this aspect of the orientation and temperature dependence of the plastic deformation of fcc single crystals. The work-hardening characteristics of single crystals of aluminum of ( 110) orientation have been studied at room temperatur "'12 and above." They have not been studied at temperatures where the virgin flow stress is dependent on temperature or where, in Seeger's terminology is important. The work hardening of single crystals of (110) orientation is of interest for another reason. As shown in Table I, the dislocation reactions that are possible in the (110) orientation are similar in certain respects to those that are possible in the (100) orientation. Hence, the deformation of single crystals of silver of (110) orientation was studied in the temperature range 100° to 900°K at intervals of 200°K. The effect of solute concentration on the plastic deformation of fcc single crystals of single-slip orientation has been studied by several investiaators.> In all of these investigations—with the exception of Ref. 20—single crystals of identical orientation have not been used, with the result that the orientation dependence of plastic deformation is superimposed on the effect of the solute. In addition, the effect of the solute on the work-hardening characteristics of single crystals of multiple-slip orientations has not been studied by the previous

Jan 1, 1965

By W. G. Matteson

The Oklahoma legislature recently passed a bill providing for "the creation of an oil and gas department under the jurisdiction of the Corporation Commission, authorizing the Corporation Commission to appoint a chief oil and gas conservation agent, and conferring exclusive jurisdiction on the Corporation Commission in reference to the conservation of oil and gas, and the inspection of gasoline and oil, the product of crude petroleum, and repealing all acts or parts of acts in conflict therewith and declaring an emergency." Some of the functions of the new bureau include the receiving and filing of all well logs, and the direction and supervision of plugging all abandoned oil and gas wells, under rules prescribed by the Corporation Commission. The two leading petroleum-producing States of the country, Oklahoma and California, have now established oil and gas bureaus with a staff of inspectors to see that the important rules relating to the conservation of oil and gas are thoroughly enforced. The economic significance and the value of well logs in the conservation work has been recognized, and the necessary legal action taken to insure and procure them. William B. Heroy, of the Government Land Classification Board, in a personal communication to the writer, says that the drilling of wells is also regulated by public authority in the Roswell artesian basin in southeastern New Mexico, where a permit must be obtained for the drilling of any well and a certified log of the well recorded with a county official. The method is said to give fairly satisfactory results. In a recent article1 a National instead of a State Bureau was suggested for collecting and filing well logs. In discussing the paper, L. L. Hutchison characterized such a plan as impractical because the average driller or contractor will often juggle or guess at the log and will not keep the record sufficiently close or accurate, making it necessary to maintain a special man at each well for the sole purpose of obtaining

Jan 1, 1918

By G. Hileman

During the year 1934 there were no new or extraordinary developments in the proven fields. With few exceptions all companies operating in these fields continued intensive exploitation programs on their old properties in an attempt to maintain the normal production of former years. In one or two instances these exploitation activities have had such marked success that the total production for 1934 slightly surpassed that of 1933. The most striking increase in production is that shown by the Kilometer 27 pool of the Comodoro Rivadavia field. However, this increase cannot be attributed to intensive drilling, since it is the result of a more uniform daily withdrawal distributed among all the productive wells. The Province of Salta also showed another increase, so that, judging from the statistics of the past three years and in view of proposed exploration projects, the future may reveal some interesting developments in this province. One of the most interesting occurrences in Salta is the discovery, though not yet considered commercial, made at Macueta, near the boundary line between the Argentine and Bolivia. This exploration well was drilled by the Standard Oil Co. of New Jersey and is the northernmost exploratory well in the republic. The oil from this well is of the same type and commercial value as that produced in the San Pedro and Lomitas fields. The producing horizon is also the same as that in the other Salta fields; that is, the Paleozoic Permo-Carboniferous.

Jan 1, 1935

By D. S. Flett, D. W. West

The solvent extraction of chromium 111 has been studied for the system Cr 111, H,SO., H,O/RNH/RNH., xylene, where the primary amine used was Primene JMT. Rate studies have shown that extremely long equilibrium times are required, ranging from 1 hr at 80°C to 20 days at room temperature. Heating the solution prior to extraction increases the rate of extraction. The variation in the amount of Cr 111 extracted is an inverse function of the acidity of the aqueous phase. Thus, the slow rates of extraction appear to be connected with the hydrolysis of the Cr I11 species. Extraction isotherms for the extraction of Cr 111 have been obtained for two sets of experimental conditions, namely at 60°C and for a heat-treated solution cooled to room temperature. The separation of Fe 111 from Cr 111 and Cr 111 from Cu 11 in sulfate solution by extraction with Primene JMT has been studied and shown to be feasible. A survey of the literature relating to the solvent extraction of chromium showed that, although many systems exist for extraction of Cr VI, only a very few reagents have been found to extract Cr 111. The extraction of Cr III by di-(2-ethyl hexyl) phosphoric acid has been reported by Kimura.' A straight-line dependence of slope —2 was observed between log D,, and the log mineral acid concentration at constant extractant concentration. Since the slope of this plot reflects the charge on the ion extracted, it must be concluded that a hydrolyzed species of Cr III is being extracted. Carboxylic acids generally do not form extractable complexes with Cr III but di-isopropyl salicylic acie does extract Cr 111. Simple acid backwashing of the organic phase, however, failed to remove the chromium. Similar difficulty in backwashing was found by Hellwege and Schweitzer8 in the extraction of Cr I11 with acetyl-acetone in chloroform. The extraction of Cr 111 from chloride solutions by alkyl amines has been reported4-' but the maximum amount of extraction achieved in these studies did not exceed 10%: From sulfate solutions, however, Ishimori" has shown that appreciable amounts of Cr I11 were extracted by amines. The amines used were tri-iso-octyl amine, Amberlite LA-1 (a secondary amine, Rohm & Haas) and Primene JMT (primary amine, Rohm & Haas). The efficiency of extraction with regard to amine type was primary>secondary> tertiary. Appreciable extraction of Cr I11 was recorded for Primene JMT as the aqueous phase acidity tended to zero. The major difficulty with Cr I11 in solvent extraction systems stems from the nonlabile nature of the ion in complex formation. This accounts for the slow rate of extraction generally experienced and the difficulty encountered in backwashing the Cr I11 from the organic phase in the case of liquid cation exchangers. Consequently, the possibility of extraction of Cr I11 as a complex anion is attractive since the backwashing problems should be minimized in this way. From published data, it appeared that the extraction of chromium from sulfate solutions of low acidity by primary amines afforded the best chance of success for a useful solvent extraction system for Cr iii This paper presents the results of a study of the extraction of Cr I11 from sulfate solution by Primene JMT and examines the application of such an extraction procedure for the recovery of chromium from liquors containing iron and copper. Experimental Chromium solutions were prepared from chrome alum in sulfuric acid and sodium sulfate so as to maintain a constant concentration of sulfate ion of 1.5 molar. Solutions of Primene JMT were prepared in xylene and the amine equilibrated with sulfuric acid/sodium sul-fate solutions, of the same acidity as the chromium solution, until there was no change in acidity between the initial and final aqueous phases. The solutions of Primene JMT conditioned in this way were then used for the equilibration experiments. Equilibrations at 25°C were carried out in stoppered conical flasks shaken in a thermostat; equilibrations at all other temperatures were carried out in stirred flasks in a thermostat. After equilibration, the phases were separated and analyzed for chromium. In the tests on the rate of extraction, small samples of equal volume of both phases were withdrawn from time to time and the chromium distribution determined. The chromium analyses were carried out either coloi-imetrically using diphenyl carbazide, or volu-metrically using addition of excess standard ferrous ammonium sulfate and back titration of the excess iron with potassium dichromate. The oxidation of Cr 111 to Cr VI in the case of the raffinate solution was effected by boiling with potassium persulfate in the presence of silver nitrate and, for the backwash solution, by boiling with sodium hydroxide and hydrogen peroxide. Results Preliminary experiments indicated that extraction results were effected by the age of the chromium solution, higher distribution coefficients being obtained with solutions which had been allowed to stand for some time. Consequently a stock solution of chrome alum, 10 m moles per 1 Cr I11 in 1.4 M Na,SO,/O.l M &SO,,

Jan 1, 1971

By Philip M. Mc Kenna

When a new material becomes available to industry, it is useful to describe its properties as a guide to its most effective application; and when the new material may be produced in compositions having a series of graded properties, tests to select the combination of properties best adapted for various uses are helpful. The class of materials to be considered in this paper are hard tool materials produced by processes of powder metallurgy from hard carbide constituents and various matrices of iron, nickel or cobalt, or alloys of them with tungsten, or tungsten and carbon. The customary use of carbide hard alloys is for metal-cutting tools; although wire-drawing dies, lathe centers, follow rests, grinding rests, burnishers, rolls, extrusion dies, measuring gauges and micrometers, and a number of other tools are also made with these hard alloys as the essential wear-resisting parts. The properties and tests to be considered are those affecting these uses. In the development of tool materials since the industrial revolution we have had carbon tool steels, Mushet steel, high-speed steels, stellites, and now cemented carbide compositions. For an understanding of the latter category of materials their properties and uses relative to the older and more familiar tool materials will be considered. Hardness has been the property of greatest practical interest in tool materials. The word "hardness" is a generalized term lacking definite-ness unless the specific test used is described. However, efforts to explain physical properties as a consequence of chemical bond, and distance between atoms in chemical compounds have been illuminating. This seems the most generalized attack on the problem, and is based upon the idea that atoms in a lattice are held together as the square of the valence and inversely as the square of the distance between the atoms. The compounds compared must all be of the same crystalline arrangement. 100 W2 It is interesting to note the values of the figure 7 A 3 /3for a number of

Jan 1, 1938

By Philip M. Mc Kenna

When a new material becomes available to industry, it is useful to describe its properties as a guide to its most effective application; and when the new material may be produced in compositions having a series of graded properties, tests to select the combination of properties best adapted for various uses are helpful. The class of materials to be considered in this paper are hard tool materials produced by processes of powder metallurgy from hard carbide constituents and various matrices of iron, nickel or cobalt, or alloys of them with tungsten, or tungsten and carbon. The customary use of carbide hard alloys is for metal-cutting tools; although wire-drawing dies, lathe centers, follow rests, grinding rests, burnishers, rolls, extrusion dies, measuring gauges and micrometers, and a number of other tools are also made with these hard alloys as the essential wear-resisting parts. The properties and tests to be considered are those affecting these uses. In the development of tool materials since the industrial revolution we have had carbon tool steels, Mushet steel, high-speed steels, stellites, and now cemented carbide compositions. For an understanding of the latter category of materials their properties and uses relative to the older and more familiar tool materials will be considered. Hardness has been the property of greatest practical interest in tool materials. The word "hardness" is a generalized term lacking definite-ness unless the specific test used is described. However, efforts to explain physical properties as a consequence of chemical bond, and distance between atoms in chemical compounds have been illuminating. This seems the most generalized attack on the problem, and is based upon the idea that atoms in a lattice are held together as the square of the valence and inversely as the square of the distance between the atoms. The compounds compared must all be of the same crystalline arrangement. 100 W2 It is interesting to note the values of the figure 7 A 3 /3for a number of

Jan 1, 1938

By Bunting S. Crocker

DISCUSSION Fred C. Bond (Allis-Chalmers Manufacturing Co., Milwaukee)—This is a very complete description of the screened ore fine grinding installation at Lake Shore. The only important data which might be desired are the operating screen analyses and power consumption in each stage. The statement that the energy consumption, or kw-hr per ton, remains constant for all mill diameters is of great interest, but the opinion is widely held that the kw-hr per ton decreases as the mill diameter increases. More definite test work is needed to establish this point. Screened ore fine minding has been successful on hard Lake Shore ore &d on about equally hard South African Rand ore. However, it is still not determined whether it would be successful on ores of average or less than average hardness. It is possible that with softer ores the consumption of ore pebbles might be exceedingly high, or might even exceed the available supply. Also, the softer feed might result in a rapid buildup of harmful intermediate sizes in the mill circuit. These factors can be determined only by a full scale or long pilot mill test. In any case the Lake Shore staff is to be congratulated for this pioneering work. Bunting. S. Crocker (author's reply)—As requested, the operating screen analyses and Bower consumption for each of the four stages of pebble milling are given, see Table XII. The fist three stages are in series circuit; the last stage is in closed circuit. The primary circuit had rock feed averaging 124 g per piece and the final stages rock feed weighing 63 g. The intermediate stages had mixtures of the two. Regarding Mr. Bond's statement that "the opinion is widely held that the kw-hr per ton decreases as the mill diameter increases," I would say that I have frequently been told this but have never yet been shown any evidence or seen any evidence published that would prove this statement. It may be true that some of the big mills recently installed have mechanical power savers such as micarta bearings and better lubrication, but as far as the power consumed inside the mill is concerned, we at Lake Shore think that it varies as D2 .", and that is all. We published extensive information on this point in our 1939 paper. Recently Mr. Banks at Consolidated published the figures on his 10 ft 8 in. x 12 ft 0 in. rod mill. As reported in this discussion by the writer: we calculated the power necessary to run this mill based on our 7x6-ft rod mill to within 1 pct of the actual power reported by Mr.

Jan 1, 1953

By Bunting S. Crocker

DISCUSSION Fred C. Bond (Allis-Chalmers Manufacturing Co., Milwaukee)—This is a very complete description of the screened ore fine grinding installation at Lake Shore. The only important data which might be desired are the operating screen analyses and power consumption in each stage. The statement that the energy consumption, or kw-hr per ton, remains constant for all mill diameters is of great interest, but the opinion is widely held that the kw-hr per ton decreases as the mill diameter increases. More definite test work is needed to establish this point. Screened ore fine minding has been successful on hard Lake Shore ore &d on about equally hard South African Rand ore. However, it is still not determined whether it would be successful on ores of average or less than average hardness. It is possible that with softer ores the consumption of ore pebbles might be exceedingly high, or might even exceed the available supply. Also, the softer feed might result in a rapid buildup of harmful intermediate sizes in the mill circuit. These factors can be determined only by a full scale or long pilot mill test. In any case the Lake Shore staff is to be congratulated for this pioneering work. Bunting. S. Crocker (author's reply)—As requested, the operating screen analyses and Bower consumption for each of the four stages of pebble milling are given, see Table XII. The fist three stages are in series circuit; the last stage is in closed circuit. The primary circuit had rock feed averaging 124 g per piece and the final stages rock feed weighing 63 g. The intermediate stages had mixtures of the two. Regarding Mr. Bond's statement that "the opinion is widely held that the kw-hr per ton decreases as the mill diameter increases," I would say that I have frequently been told this but have never yet been shown any evidence or seen any evidence published that would prove this statement. It may be true that some of the big mills recently installed have mechanical power savers such as micarta bearings and better lubrication, but as far as the power consumed inside the mill is concerned, we at Lake Shore think that it varies as D2 .", and that is all. We published extensive information on this point in our 1939 paper. Recently Mr. Banks at Consolidated published the figures on his 10 ft 8 in. x 12 ft 0 in. rod mill. As reported in this discussion by the writer: we calculated the power necessary to run this mill based on our 7x6-ft rod mill to within 1 pct of the actual power reported by Mr.

Jan 1, 1953

Merritt: Karl, you are a native New Englander, having been born in St. Albans, Vermont, in 1885. How did you decide on becoming a mining engineer? Twitchell: While I was attending St. Albans High School, my uncle, who had been the American Consul in Kingston, Ontario, for many years, told me of the excellent mining school there. He also introduced me to a Canadian mining engineer who sparked my interest in mining by noting the possibility of achieving personal success without always being under salary. Well, that appealed to me, so I applied to the Kingston School of Mines at Queen's University.

Jan 9, 1965

By E. A. Has, E. Mcl. Tittmann

Double roasting of sinter carrying a high percentage of lead concentrates, gave rise to the problem of removing the sheets of metallic lead formed in the wind boxes. The solution of the problem has been found in the water sealed wind boxes. The metallic lead is granulated and can be removed without seriously interfering with the operation of the machine and eliminates necessity of men going in wind boxes with air guns. THE practice of double sintering the charge for lead blast furnaces, which is now standard throughout the lead smelting industry, has introduced the rather difficult problem of cleaning the wind boxes on sintering machines used for the final pass. Two factors have more recently accentuated this problem: (1) the growing demand of workmen for better working conditions and less arduous labor, and (2) the growing dearth of crude lead ores and the improved grade of lead concentrates demand a charge carrying the maximum percentage of lead. One to 2 pct of such high lead charges (30 to 40) when processed on machines in reasonably good condition will pass through the grates and report in the wind boxes. One-half to three-quarters of this material will be metallic lead reduced by the coke breeze or other fuel mixed with the charge. This lead forms large cakes or chunks which are hard to remove and which substantially increase the time the machine is out of operation for cleaning the wind boxes. A high lead fall can reduce the operating time 30 pct. As a specific example, a 30 ft machine having 63 in. pallets, and equipped with three conventional wind boxes, requires 3 to 4 hr per day for removing the accumulation in the wind boxes when operated as a final pass machine. This same machine when operated on raw charge requires less than an hour per day for cleaning. To eliminate formation of large chunks of lead in the wind boxes of the final pass machines and time lost in cleaning the boxes, R. C. Rutherford of the Chihuahua smelter of the American Smelting and Refining Co., devised and patented* a wind box having a water bath to granulate the lead as it falls from the grate bars. Later, C. H. Harris of the San Luis plant made and patentedt an improvement on Rutherford's device in which the water bath seals the wind box in a manner permitting the latter to be readily cleaned without destroying the vacuum. The first machine to our knowledge to use the water bath box was at the Chihuahua plant along the lines of the Rutherford patent. In 1942, a machine was placed in operation at the El Paso plant which incorporated the features of both Rutherford and Harris. This machine is 40 ft long equipped with pallets 63 x 24 in., and having 4 wind boxes 10 ft 4 in. x 7 ft 2 in. x 51 ft 3 in. in size (fig. 1). The air from the fourth box is returned to the first three, and the gas from the first three discharged to a baghouse. The machine has conventional drive, discharge hopper,

Jan 1, 1951

By W. Tovote

THIS paper is based upon 12 years' experience in the Southwest, including three years that were spent in constant traveling as examining engineer for the Phelps-Dodge Corporation. The material was gathered during rather extensive work in Bisbee, Clifton-Morenci, Globe, and Tombstone, and also on short and rapid trips into most of the mining camps and prospect fields of New Mexico, Arizona, the desert country of California, and as much of Sonora as was safe at the time. My methods of observation and my deductions are not put forward as new or scientific; they are simply rough field methods, based upon short notes, rough sketches, and largely upon memory, which I have found useful for coordinating geological data for the purpose of passing quick judgment on mining possibilities in certain districts exhibiting uniform characteristics. The opportunities for observation have been better these last few years than ever before, clue to the unprecedented activity in mining, which has caused the reopening of hundreds of old mines and the starting of even more numerous prospects all over the mining States. POSSIBLE SYSTEMS OF CLASSIFICATION By Geological Provinces There are a number of well defined geological provinces in the territory under discussion, and a study of their individual features is of interest. The following are a few of those that axe most striking in their uniformity. 1. The "Desert province," extending roughly from. Wickenburg, Ariz., to and beyond Barstow, Cal. In its north-south extent it reaches up to the Colorado River and clown into Sonora, but overlaps other provinces. It is characterized by a worn-down basement of schistose and granitic rocks, on which rest remnants of Paleozoic and pre-Paleozoic sediments, including very old limestones. The sediments are disrupted and contorted. Alteration in the mineralized areas is very prominent, especially in the schists and limestones. Cenozoic volcanic rocks, principally of semi-basic composition, have been intruded into this complex and sometimes cover it as lava flows.

Jan 10, 1918