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By R. L. Hopkins

Fifteen alkyl cycloalkyl sulfides and three dicycloalkyl sulfides were synthesized to provide reference compounds in the search for these classes of sulfur compounds in crude oils. In synthesizing sulfides by alkaline alkylation the order in which the reactants were added was shown to determine the yield and purity of the product.

Jan 1, 1966

By A. J. Forney

This report summarizes the findings of methods of treating caking coals in a fluid bed to destroy their caking properties. In batch tests it was found that several coals, including those with a free-swelling index greater than 8, could be decaed at temperatures from 400° to 425° C with a fluidizing gas composed of inert gas or steam containing 0.2 percent oxygen and a minimum residence LS,-;,' of 5 minutes. When treatment decreased the free-swelling index from about 8 to 1-1/2 or lower, the resulting treated coal was noncaking. In a continuous unit with continuous feed and discharge of coal, slightly more severe conditions were required to decake the coal. For 18- to 100-mesh coal a temperature of 430° to 440° C and an oxygen-to coal ratio of 0.4 cubic foot of oxygen per pound of coal feed was necessary. Finer mesh sizes required lower oxygen-to-coal ratios. In tests using air only as the fluidizing medium and treatment temperatures well below the softening range, the caking properties of 150- to 200-mesh coal were destroyed in 30 to 40 minutes of residence time at 200° C. Coarser sizes of 18 to 48, 48 to 100, and 100 to 150 mesh required longer residence time.

Jan 1, 1966

By Leo A. Schrider

This report analyzes the successful low-pressure gas drive in the Keener sand of the Bonds Creek oilfield, Pleasants and Ritchie Counties, W. Va.) and predicts its future performance. Core analysis from two wells and electrical and radioactivity logs were used to evaluate the reservoir characteristics. Production records over a 37-year period indicate that over 240,000 barrels of oil have been produced from the Keener sand by low-pressure gas injection. Decline-curve analysis shows that 165,000 additional barrels should be recovered from 108 acres of productive sand by continuing this secondary-recovery method.

Jan 1, 1966

By Charles M. Mason

The Bureau of Mines evaluated equipment and procedures for drop-weight testing of explosive liquids as prescribed by Test 4) a widely used method. It was demonstrated that partial ignitions, originally designated as negative results, should be designated positives; it was also shown that wear or erosion of the sample cups and the type of mount used for the apparatus had important effects on the results. Relative sensitivity as measured by Test 4 was found to vary slightly with temperature. The Bureau also designed a fixed 2-kg weight and associated electromagnetic release, which subsequently were incorporated as standard in a revision of Test 4. The original concept that the test involves only adiabatic compression was found to be an oversimplification; an alternate mechanism for the initiation process is proposed in which due consideration is given to the effects of cavitation and microjets.

Jan 1, 1966

By Robert M. Doerr

The oxidation kinetics of Ni-Y alloys in the range 0.04 to 8 weight-percent Y, and of high-purity Ni, were compared by the use of a sensitive volumetric apparatus. The reactions followed approximately the parabolic rate law; for oxidations in 02 at 0.5 atm and 1,200° C, the parabolic rate constant was about 0.37 + (0.064) (Y-2.11) mg cm-2 min-1/2, where Y represents the weight-percent Y in the alloy. Internal oxidation of Y occurred in the alloy specimens and the resultant Y203 particles, which were in patterns related to the eutectic structure of the alloys, served as markers showing that the subsequent oxidation of the surrounding Ni was by inward diffusion of O. The scale consisted in each case of NiO, but the inner parts of the scale on the alloy specimens included the patterned Y203 particles. The thicknesses of the inner parts of the scale depended directly on the Y concentration, and the thicknesses of the Y2O3-free outer parts of the scale were inversely related to the Y content of the alloys. There is thus a relationship between the thickness of the outer part of the scale and the protectivity of the scale. Outward diffusion of Ni and inward movement of 0, from the inner boundary of the Y2O3-free part of the scale, is proposed as a mechanism for these results.

Jan 1, 1966

By A. L. Service

Idaho has nearly 6 billion tons of potential sources of phosphorite, 10 to 31 percent P2O5' above and within 100 feet below entry level, the largest potential of any State in the United States. In 1963 Idaho ranked third after Florida and Tennessee in total mine and marketable production of phosphate rock; Montana ranked fourth. This report describes phosphate deposits, mines, and prospects in 10 districts covering most of the Idaho phosphate field. All mine production of phosphate rock in Idaho comes from surface mines and is processed to phosphate fertilizers, phosphoric acid, and elemental phosphorus. Producing districts are Fort Hall (Gay mine), Trail Creek (Conda and Ballard mines), and Crow Creek (Georgetown Canyon mine). FMC Corp. and J. R. Simplot Co. at Pocatello have the largest elemental phosphorus and fertilizer production facilities, respectively, in the State, followed by Monsanto Co. and El Paso Natural Gas Products Co. (formerly Central Farmers Fertilizer Co.). The only other major phosphate processing plant in the State is the phosphoric acid and phosphate fertilizer complex at Kellogg operated by the Bunker Hill Co. In 1963 a plant was constructed and put on line at Monsanto, Idaho, to recover vanadium from ferrophosphorus produced by electric furnace operations in the area. El Paso Natural Gas Products Co. completed construction of a fertilizer and phosphoric acid plant near Conda in 1965. There is a small fertilizer plant producing phosphate fertilizers for local consumption in Soda Springs.

Jan 1, 1966

By Gerald W. Elger

This report describes development of the fusion-leach crystallization precipitation process for producing a hafnium content feed material for hafnium-zirconium separation plants. Mixtures of zircon, potassium silicofluoride, and potassium carbonate (or potassium chloride) were fused to prepare soluble potassium zirconium hexafluoride-potassium hafnium hexafluoride salts. High extraction of these salts was obtained by countercurrent leaching the fused material in dilute hydrofluoric acid. About one-half of the hafnium was recovered in hafnium-enriched mother liquor by cooling clarified lead: liquor to crystallize most of the zirconium salt. Additional hafnium was recovered from the primary crystals in a multiple dissolution-recrystallization step. Hafnium-enriched oxides having a hafnium-zirconium ratio of more than three times that of zircon were precipitated from the combined mother liquors. The hafnium and zirconium recoveries in the precipitate were 83 and 24 percent, respectively. About 71 percent of the zirconium and the remainder of the hafnium were recovered in potassium zirconium hexafluoride crystals of low-hafnium content.

Jan 1, 1966

By H. J. Coleman

Knowledge of the types of naturally occurring sulfur compounds in petroleum is of both theoretical and practical interest to petroleum chemists and geologists. This knowledge has been extended by the identification of 77 sulfur compounds, including 36 thiols, 23 chain sulfides, and 18 cyclic sulfides in a 111° to 150° C boiling range distillate of Wasson, Texas, crude oil. The characterization procedure used in separating and identifying these compounds included isothermal distillation, vacuum fractionation, liquid-solid chromatography (alumina adsorption), chemical treatment, gas-liquid chromatography, microdesulfurization, and infrared analysis. The procedural steps described represent a systematic method of sulfur compound analysis considered applicable for determining the nature and concentration of the sulfur constituents present in any straight-run petroleum distillate of the above-boiling range.

Jan 1, 1966

By John M. Gomes

In the repetitive electrowinning of tungsten from scheelite, the calcium impurity buildup in the molten electrolyte results in decreased metal purity, metal recovery, and current efficiency. Periodic addition of B2O3, which reacts with the lime liberated from the scheelite, more than tripled the life of the electrolyte in winning 99.9-percent-pure tungsten and also reduced the number of units of electrolyte required per unit of tungsten recovered from six to four.

Jan 1, 1966

By Nicholls Harry R.

The Bureau of Mines studied the effect of varying the, diameter of explosive charges on the generation and propagation of strain waves. The parameters compared were strain amplitude, impulse, energy, and pulse shape. Three different explosives were detonated in three different charge diameters. Charges of cast 50/50 pentolite-detonated at the same velocity in 5-, 2.5-, and 1.5-inch diameters. Charges of ammonium nitrate-fuel oil prills and 45-percent semigelatin dynamite showed a strong detonation rate-diameter dependency. Detonation of these two explosives was considered nonideal. Differences in the diameter of the charge caused less difference in the strain-generating abilities of pentolite than in those of the other two explosives. This was also true for impulse and energy. Rise and fall times of the strain pulses for all three explosives were proportional to detonation time and cavity volume, respectively.

Jan 1, 1966

By C. W. Schultz

The vapor pressure of manganese in equilibrium with a series of liquid iron-manganese alloys was determined by the carrier gas method over a broad range of alloy composition. From these data the activities of manganese in the iron-manganese system were calculated. The system appears to be ideal.

Jan 1, 1966

By Martin H. Stanezyk

The Bureau of Mines investigated leaching of selected copper sulfide minerals and a composite of impure flotation concentrates at elevated temperatures and pressures with ammoniacal solutions. Copper 1 (tractions of 96 percent were obtained by leaching chalcopyrite at 75° C under oxidizing conditions for 60 minutes. An extraction of 99 percent of the copper contained in the composite concentrate was obtained by leaching the product for 90 minutes at 75° C. In tests of bornite, chalcocite, and covellite, 90 to 97 percent of the copper was extracted at 20° C provided an 8-hour reaction period was used. At 75° C essentially complete dissolution of the copper from these three minerals was accomplished in 60 minutes. Additions of ammonium sulfate to the leach solutions were required to obtain high-percentage extractions of the copper from bornite, chalcocite, and covellite. Although ammonium sulfate was not required when digesting chalcopyrite, copper extraction was enhanced and less free ammonia was required when ammonium sulfate was added to the leach pulps. The chemistry of leaching copper minerals was studied. It was C, termined that chalcocite altered to covellite as one step in the dissolution When leaching iron-bearing copper sulfides, hydrated iron oxide formed on the mineral surfaces, indicating that a diffusion process prevailed. No evidence of covellite was detected.

Jan 1, 1966

By D. J. Bauer

The Bureau of Mines demonstrated the feasibility of fractionating lanthanide nitrates with a tertiary amine on lanthanum-cerium and thulium-ytterbium pairs. Optimum values were determined for pH, phase concentration, and percent chelation of metal ions in the aqueous phase. Percent extraction is markedly dependent on the concentration of lithium nitrate in the aqueous phase. Selective masking of the heavier element in each extraction system with DTPA or EDTA aqueous-phase chelating agents resulted in lanthanum-cerium separation factors of 8.5 and thulium-ytterbium separation factors of 3.4.

Jan 1, 1966

By Francis X. Cannaday

The Bureau of Mines developed equipment to measure the sonic velocity of pulses transmitted through rock samples varying in size from laboratory specimens to mine pillars in place. Pulses are produced by electronically excited piezoelectric ceramic transducers. Special equipment components were developed by Bureau facilities; other components are commercially available. The technique permits a nondestructive, repetitive, stable, shaped pulse to be used in place of explosive caps or hammer blows. Longitudinal wave travel time measurements were taken on an oscilloscope screen; transverse wave measurements were taken under special field conditions. Results were consistently repeatable within the accuracy of the oscilloscopes utilized.

Jan 1, 1966

By John Nagy

The Bureau of Mines adapted thermal theories explaining combustion of gases to correlate parameters affecting ignition of dust dispersions. The dust dispersions were ignited in a Godbert-Greenwald furnace at atmospheric pressure. Ignition temperature and the concentrations of fuel, admixed inert powder, and atmospheric oxygen were related mathematically. Values for these parameters obtained in laboratory experiments for cornstarch agreed with theory. The developed equation permits extrapolation; the predicted upper igni-tion limits correspond with limited experimental data from laboratory and large-scale tests. Explanation of the effect of fineness of dust on ignition parameters is attempted by introducing a surface-area constant to modify the activation energy. Arguments are presented to show that the ignition process is a solid-gas phase reaction rather than an ignition of prevolatilized gases.

Jan 1, 1966

By V. E. Homme

Low- and high-temperature reduction techniques were employed by the Bureau of Mines in study of conditions favorable to the formation of massive titanium crystals. '1,1,2 low-temperature method, feeding molten sodium to solidified titanium lower chloride-sodium chloride, produced higher quality and high quantity crystalline metal. The percentage of crystalline titanium was increased with increasing reactor diameter, melt depth, and titanium dichloride concentration. The high-temperature technique, feed molten sodium to melts above 8000 C, producing needle-type crystals of lower quality and with less consistent results than the low-temperature method. Layers of titanium foil, sponge, fine needles, wool, and crusts of sin-tered granules were formed during the earl, -art of the low-temperature reduction, and massive crystals were produced beneath this barrier in the latter part of the reduction. Crystalline titanium having an average hardness of Bhn 76 and representing 58 percent of the total titanium was obtained. Lamellar crystals up to 1 1/2 inches long with a hardness as low as Bhn 54 were also produced. A second-stage reduction for reclaiming titanium from offgrade sponge is described. Titanium produced by this method was comparable in quality to that from sodium reduction of titanium tetrachloride.

Jan 1, 1966

By G. W. Birge

The Bureau of Mines investigated the effect of temperature on the mechanical strength of cokes of the type normally used in blast furnace operations. Eight samples of industrially produced cokes were subjected to ASTM tumbler tests at temperatures as high as 1,100° C (2,012° F); these temperatures had no significant effect on tumbler results for cokes with stability indexes of 40.6 to 59.9. Two foundry cokes which were tested at only one elevated temperature (900° C) decreased slightly in tumbler stability. Iron are pellets made from a variety of ores and by various industrial methods were not significantly affected by temperature when tested in an oxidizing atmosphere at 1,000° C (1,832° F) by the tentative standard ASTM method.

Jan 1, 1966

By R. E. Coleman

The molecular species occurring at the mineral-reagent interface of the galena-aqueous potassium ethyl xanthate system was studied by developing a technique for using an attenuated reflection method in conjunction with standard infrared spectroscopy procedures. Lead ethyl xanthate was detected from the infrared spectra of all galena surfaces treated in the pH range of 7 to 11. At pH 8.5, lead ethyl xanthate formed as a film chemically bonded to the galena surface. A solvent extraction sampling method was employed with infrared spectroscopy to obtain quantitative data on the lead ethyl xanthate removed from the galena surface. The data showed that between pH 7 and 11 thy quantity of lead ethyl xanthate physically adsorbed decreased as the pH was decreased; in the same pH range, the quantity of free lad ethyl xanthate in the aqueous medium remained constant, and the amount of unreacted xanthate varied.

Jan 1, 1966

By Jack G. Croeni

The Bureau of Mines developed a method to extrude low-density tungsten powder billets into rods and sheet bar with high-energy-rate forming equipment. Billets were compacted and sintered in an atmosphere of hydrogen to obtain a density of approximately 60 percent. Extrusion was conducted at reduction ratios of 6.25 to 1 and 9 to 1 at 1,800° C to prod e high-density, sound material. Yield strengths obtained were higher than those of material produced by conventional powder-metallurgy techniques, but ductility was lower at high temperatures.

Jan 1, 1966

By M. M. Wong

Salt mixtures consisting of KC1, BaC12, and HfCl4 with RbCl or CsCl were investigated as electrolytes for refining hafnium. The presence of RbCI or CsCl in the electrolyte appeared to suppress the volatility of. Best electrorefining was obtained with an electrolyte containing 50.7 percent KCl, 27.l percent BaCl2, 15.7 percent CsCl, and 6.5 percent HfCl4. In this electrolyte, hafnium metal with an average oxygen content of 470 ppm was produced from an anode feed containing l,600 ppm oxygen. All metallic impurities were lowered, except titanium, manganese, and tin.

Jan 1, 1966