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By Donald I. Bleiwas

The U.S. Bureau of Mines has evaluated the potential availability of nickel from 36 deposits or districts in 16 market-economy countries (MECs), analyzing more than 95 percent of production in those countries. This study indicates the quantity of nickel available on the basis of net production costs and total costs with a 0-pct and a 10-pct discounted cash flow rate of return (DCFROR). Costs of production are expressed in dollars per pound of recovered nickel. The study also indicates sensitivities of the cost of production to energy, labor, and other factors. The studied deposits and properties contain approximately 33 Mmt of recoverable nickel. About 26 Mmt of nickel is potentially recoverable from laterite deposits, of which 4.5 Mmt can be produced at $2.50/lb or less with a 0-pct DCFROR. Approximately 7 Mmt of nickel is potentially recoverable from sulfide deposits, of which about 6.3 Mint could be produced at $2.50/lb or less at a 0-pct DCFROR. The price of nickel averaged above $6.00/lb in 1988. Sensitivity studies performed for both laterite and sulfide deposits indicate that the total cost of producing nickel from laterites is most sensitive to increases in energy costs and that the total cost of producing nickel from sulfide deposits is most sensitive to increases in labor costs; sulfides are also affected by changes in revenues from byproducts.

Jan 1, 1991

By J. J. Cummins

The Bureau of Mines heated at 150° to 350° C for 0.5 to 360. days Green River oil shale that had been previously extracted by benzene to provide information on in situ processing conditions, to determine the effect of low-temperature heating on the unconverted kerogen, and to determine the composition of benzene-soluble thermal products. The methods used in determining the composition of the soluble thermal products consisted of fractionation of the soluble material, elemental analysis of the soluble products, fractionation of the polar resins by ion-exchange chromatography, gas chromatographic analysis of [n]-alkanes3 and mass spectral analysis of the branched plus cyclic alkanes and aromatic oils. The methods used to determine the effect of low-temperature heating on the unconverted kerogen remaining in the oil shale heated residues consisted of carbon-hydrogen analysis, volatile material determination, carbon residue determination, and oxidation rate determination. In general, it was concluded that significant increases in the degradation of kerogen to oil occurred between the temperature range of 250° to 350° C; that the composition of the soluble products depends upon the temperature at which they are formed; and that the [n]-alkanes are pyrolytically degraded from the kerogen structure. In particular, the 250° C heating temperature is beneficial to the formation of branched plus cyclic alkanes. Also, the heated and unconverted oil shale kerogen and the soluble thermal products become more aromatic as the temperature increases from 150° to 350° C.

Jan 1, 1974

By H. R. Appell

The Bureau of Mines studied the conversion of a variety of cellulosic wastes, for example, sawdust, bovine manure, sewage sludge, urban refuse (free of metal and ceramics), etc., to heavy oils. The objective of the investigation was to determine the scope of the reaction and elucidate the chemistry involved. The reactions took place in the presence of synthesis gas and water or carbon monoxide and water under conditions of elevated temperatures and pressures. Waste conversions above 90 pct, often near 99 pct, with oil yields in the range of 40 to 60 pct, were obtained in the temperature range of 250° to 425° C and pressure range of 1,500 to 4,000 psig. Because mild conditions were sought, most of the experiments were conducted at temperatures of 250° to 350° C and pressures of 1,500 to 3,000 psig. In general, lower viscosity products were obtained at higher reaction temperatures. Conversions and oil yields were significantly increased by operating in the presence of a high-boiling oil; either anthracene oil or oil recycled from the process was satisfactory. Synthesis gas containing 50 pct carbon monoxide gave satisfactory results as a replacement for carbon monoxide. Cobalt molybdate on alumina catalyst, used with sodium carbonate, gave a product of lower viscosity and lower oxygen content than sodium carbonate used as the sole catalyst. The waste-to-oil process has been successfully investigated in continuous flow equipment as well as in batch autoclaves.

Jan 1, 1975

By G. E. Walden

The Bureau of Mines is currently engaged in a continuing investigation of the thermodynamic properties of certain inorganic compounds. As a part of this investigation, the heat contents of bismuth and cerous chlorides were measured throughout the temperature ranges of 370° to 630° K. and 370° to 1,200° K., respectively. Equations representing heat contents as a function of temperature were derived from the data by the method of least squares. These equations were used to calculate heat contents at selected temperature intervals ranging from the ice point to 650° K. for bismuth chloride and to 1,200° K. for cerous chloride; also, the heats of fusion of both compounds were calculated at their respective melting points. EXPERIMENTAL Materials The cerous chloride used in this investigation was supplied by the National Carbon Company of Cleveland, Ohio. A chemical analysis indicated Ce 56.57 percent and Cl 43.39 percent. No attempt was made to purify the compound or identify impurities since the analysis showed only about 0.04 percent total impurities. Reagent grade bismuth chloride was used without additional purification.

Jan 1, 1961

By J. S. Browning

The Bureau of Mines investigated the concentration characteristics of high-clay sylvinite ores from potash companies operating in the Permian basin near Carlsbad, N. Mex. These ores, containing 14 to 19 percent K20 and 3 to 5 percent clay slimes, cannot be effectively processed by current commercial flotation methods because of their high clay content. A solution to this problem was shown to be the use of two-stage moderate scrubbing conditions for clay disaggregation and removal as opposed to strenuous attritioning. Bench-scale beneficiation techniques for recovering potash minerals by flotation from the scrubbed material resulted in acceptable product grades and recoveries. By using a coarse grind, emphasis was placed on production of premium granular and coarse products. Flotation results showed that concentrates of 59.6 to 60.4 percent K.0 values can be obtained. Continuous pilot plant beneficiation techniques for recovering potash minerals by flotation resulted in concentrates containing 58.8 to 59.8 percent K20 with recoveries of 69.7 to 81.4 percent of the K20.

Jan 1, 1975

By K. O. Bennington

The thermodynamic properites of petalite (Li2A12Si8O20) were determined by the Bureau of Mines. The enthalpy of formation was determined by hydro-fluoric acid solution calorimetry. The values from the elements and from the oxides are ?Hf°298.15 = 2,335.8 ± 3.0 kcal/mole and ?H°295 (from oxides) = -50.60 ± 1.20 kcal/mole. Low-temperature heat capacities were determined by adiabatic calorimetry from 10.69 to 302.11 K. The derived standard entropy is S°298.15 = 111.0 ± 1 cal/deg-mole. Enthalpy increments above 298 K were measured by copper block calorimetry from 298 K to 1,193.6 K. The various experimental data were combined with other data from the literature to calculate the Gibbs energies of formation and equilibrium constants of formation over the temperature range of the measurements. Tables of enthalpies of formation and Gibbs energies of formation are given as a function of temperature from the elements and constituent oxides. The Gibbs energy of formation is ?G°f298.15 = 2,203.8 kcal/mole.

Jan 1, 1980

By K. K. Kelley, W. W. Weller

Heat capacity measurements of akermanite ( Ca,MgSiO ) , cordierite (Mg2A14 Sig018 ) , gehlenite ( Ca₂Al₂ SiO ) , and merwinite ( Ca ,MgSiO ) were conducted over the temperature range from 50 ° to 298.15 ° K. The entropies at 298.15 K ( expressed in cal / deg mole ) were evaluated as follows : Akermanite , 50.0 ± 0.5 ; cordierite , 97.3 ± 0.9 ; gehlenite , 47.4 ± 0.4 ; and merwinite , 60.5 ± 0.5 . All four compounds have positive entropies of formation from their constituent oxides at 298.15 ° K ; the values range from 4.6 cal /deg mole for akermanite to 10.1 cal / deg mole for cordierite .

Jan 1, 1963

By John C. Edwards, Gene F. Friel, John J. Opferman, Robert A. Franks

A series of diesel fuel fire experiments were conducted in the Pittsburgh Research Center's Safety Research Coal Mine (SRCM) to determine products-of-combustion (POC) spread rates along a single entry under zero imposed airflow conditions. Six experiments with an average fire intensity of 330 kW and three experiments with an average fire intensity of 30 kW were conducted in a 1 80 m long entry which had an average 2 m height and 4 m width. POC spread rates were measured by the response time of diffusion type CO detectors, positioned at 30 m intervals, to CO concentrations 5 ppm above ambient. For the 330 kW fires, average POC spread rates of 0.22, 0.13, and 0.06 m/s were determined at 30.60, and 90 m distances from the fire. For the 30 kW fires these average spread rates were reduced to 0.08, 0.04, and 0.04 m/s. The measured maximum roof layer temperature 30 m from two of the 330 kW fire was 30 and 36"C, which is less than the 57°C alarm point of a typical mine thermal sensor. It was determined that smoke detectors can be more effective for mine fire detection than CO detectors. The experimentally determined POC spread rates can be used to provide guidance for specification of sensor spacing to improve early fire detection at zero or very low air flows.

By Homer J. Ballinger

During the fall of 1943 and spring of 1944, the Bureau of Mines investigated nine secondary limonite iron-ore deposits in the Williamsville district of Wayne, Butler, and Ripley counties, Mo., by rotary-bucket and power-auger drilling test pitting, and trenching. Studies on beneficiating the ores were made at Bureau laboratories. Iron ore has been mined in Missouri since 1825, and iron mining reached its greatest development between 1870 and 1890. During this period, production averaged about 250,000 tons annually.

Jan 1, 1948

By L. B. Pankratz

The heat contents of the sesquioxides of erbium, holmium, thulium, and ytterbium (Er203, Ho203, Tm203, and Yb203) in the cubic crystalline form were measured over the temperature range from 298° to 1,800° K. The erbium and holmium sesquioxides gave regular heat content-temperature curves. Thulium sesquioxide had a minor thermal anomaly near 1,680° K, with a heat absorption of 310 cal/mole; similarly, ytterbium sesquioxide had a minor anomaly near 1,365° K, with a heat absorption of 150 cal/mole. The heat content results are presented in both tabular form (at 100° intervals) and in algebraic form. Entropy increments, corresponding to the tabulated heat content results, also are listed.

Jan 1, 1963

By K. O. Bennington

The thermodynamic properties of aegirine, of composition [(Na0.869Fe30+7362 Fe20+16Mn0.03Ca0.1121)(A10.141Sil 9738)(06)], were experimentally determined at the Bureau of Mines as part of its efforts to advance minerals technology. The standard enthalpy of formation determined by hydrofluoric acid solution calorimetry is AHf298 = -641.12±0.73 kcal/mol. The standard enthalpy of formation from the oxides is AH298 = -37.136±0.509 kcal/mol. Low-temperature heat capacities were determined by adiabatic calorimetry from 19.1 to 304.6 K. The derived standard entropy is S298 = 38.03±0.14 cal/mol?K. The heat capacity was measured over the range 348 to 1,198 K by differential scanning calorimetry. These experimentally determined data were combined with data from the litera¬ture to calculate the Gibbs energies of formation and equilibrium constants of form¬ation over the temperature range of the measurements. Standard enthalpies of forma¬tion are given as functions of temperature. The standard Gibbs energy of formation at 298.15 K is AGf298 = -600.36 kcal/mol.

Jan 1, 1984

By Loyal Clarke, H. H. Storch

"The discovery of large deposits of polyhalite (K2S04.MgS04.2CaSO4.2H2O) in Texas has led to an investigation of possible industrial proecsses for the extraction of potash from this material. This mineral was first discovored in small quantities in the European potash deposits in or about the year 1800. Chemists fire thought it to be a form of calcium sulphate, but a more accurate analysis by Strohmiyer indicated the composition as given by the above formula.The decomposition of polytalite by aster is very slow and results in the formation of a layer of gypsum at the surface of the polyhalite which retarts the solution of the potaseium and magnesium sulphates. To obtain a substantial yield of K2S04 in solution it is necessary to use large amounts of water at room temperature, for he concentration of K2S04 is limited by the low solubility of syngonite (K2S04.CaS04.H2O) whereas at 100º C. several days boiling are necessary to obtain more than a 6 per cent K2S04 solution even when finely powdered polyhalite is employed.In 1854 H. Rose discovered that calcination, followed by leaching with water, resulted in a larger extraction of the potassium and magnesium sulphates, as compared with leaching without precalcination. During the course of a series of investigations concerning formation of oceanic salt deposits, Van't Hoff and his pupils obtained sufficient data to construct the equilibrium diagram for the system K+Mg+SO4--Ca++.H2O for 25° C. and for 83° C. These data are very well summarized. in the International Critical Tables' and by Boeke and Eitel. From a consideration of the diagrams for 83º C. one would conclude that an extraction of polyhalite with moderate amounts of water at 33º C. would result in a solution whose maximum concentration of K2So4 would be about 3.6 grams per 100 grams of water and of M2SO; about 4.0 grams per 100 grams of water, corresponding to equilibriumwith the solid phases: Polyhalite potassiam-calcium pentasulphate and anhydrite.The fact that it has been found possible to obtain as high as 11.4 grams of K2S04 per 100 grams of water (see table 6) and an equivalent amount of MgSo4 (8.1 grams per 100 grams of water was obtained corresponding to a ratio K2/Mg of 0.98; indicates that the formation of these complex salts is very slow. To be sure, this results was obtained at 100° C. instead of 83º C. However, the work of Anderson and Nestall 9 on the double salts of calcium and potassium sulphates at 100º C. indicates that the diagram at 100º C. C. would not be greatly different from that at 83º C. This slow rate of approach to equilibrium when combined with precalcination of,of polyhzli-,a is the 17,asis of some of the more p:olisinE methods of extracting potash from polyhalite."

Jun 1, 1930

By M. J. Ferrante

Relative enthalpies of V20S from 298.15 to 1,101.0 K were measured at the Bureau of Mines to provide data needed for the advancement of min-eral technology. Enthalpies were measured with a copper-block calorimeter. A sharp melting point was found at 951 K, with [~~ = 15.690 kcal/ mol ] for the standard enthalpy of melting. Tabulated values are given at selected temperature increments between 298.15 and 1,500 K for the standard relative enthalpy [(HO -H~98),] heat capacity (CpO), entropy (SO), and Gibbs energy function [-(Go -H298)/T]. Standard relative enthal-pies are also given in equation form and combined with data from the literature to derive values of standard enthalpies of formation and Gibbs energies of formation.

Jan 1, 1986

By John C. Edwards

The Bureau of Mines has developed a time-dependent mathematical model of radiative heating of bulkheads in mines. The model includes both reradiation from the duct (cylindrical) walls and direct radiation from the fire zone. Thermal loss into the wall of the duct and into the bulkhead is included. Both brick and wood bulkheads are considered. It is found that the heating rate of the system scales as the duct length-to-diameter ratio and the flame temperature. In particular, the time required for the irradiated surface of the bulkhead to reach a specified temperature decreases with increasing flame temperature for a fixed length-to-diameter ratio and increases with increasing length-to-diameter ratio for a specified flame temperature. It is also deter-mined that the time, T, for the bulkhead surface temperature to reach a specific value, Tb, for a fixed length-to-diameter ratio less than 4 and for a flame temperature of 1,200 K is approximately linearly dependent on Tb for 500 K < Tb < 700 K, and is nearly exponentially dependent on the length-to-diameter ratio for Tb = 600 and 700 K.

Jan 1, 1979

By Steven J. Page, John A. Organiscak

Airborne dust generation is one of the byproducts of coal mining, processing, and handling. The amount of airborne total dust (ATD, respirable size and larger) and airborne respirable dust (ARD) generated is of primary interest for designing the level of engineering controls needed for adequate dust abatement. Laboratory crushing experiments were conducted in a wind tunnel with a roll crusher to identify relationships among crushing parameters, product size, coal rank properties, and airborne dust generation. Through the first series of experiments, the effect of primary and secondary breakage processes on both product size and airborne dust generation was examined. Through a second series of experiments, the effect of coal rank properties on product size and airborne dust generation was studied using a uniform crushing process with secondary breakage. Laboratory results indicate that secondary breakage of a particular coal notably increases the specific amount of ATD generated, while negligibly impacting the specific amount of ARD generated. A strong positive relationship was identified between the specific amounts of ATD and ARD generated during the primary breakage process (with minimal secondary breakage), but a negligible relationship was observed between the same two variables when secondary breakage was introduced into the crushing process. This indicates that most of the ATD and ARD is generated from the primary breakage, while secondary breakage has a more of an influence on generating additional amounts of larger sized ATD. Additional experiments involving the uniform crushing of eight different bituminous coals showed that the coal rank, expressed as the inherent moist fuel ratio (MFR = fixed carbon =(volatile x inherent moisture)), had diverse relationships between the product size created and the amount of airborne dust generated. As bituminous coal rank or MFR increased, the amount of coal product fines < 250 gm increased while the mass percentage of ATD and ARD liberated from these < 250 µm product fines decreased. Air dry loss (ADL) moisture in the coal was found to be inversely related to the dust cloud electrostatic field, influencing dust liberation from the coal product fines. Since the MFR was directly related to the dust cloud electrostatic field, opposite the ADL-electrostatic field relationship, the diverse relationships between the product size created and the amount of dust liberated from the < 250 µm product fines were explained. Finally, 12 to 14 times more ATD was generated as compared to the ARD generated during these experiments. These results should provide a fundamental basis for initial estimation of the airborne dust loading requirements of engineering control methods for coal crushing.

By Mary H. Brown

The heats of formation of oxalic acid and sodium, potassium oxalates, and lithium oxalates were related by solution calorimetry to the heat of formation of (COOH)2.2H20, a value believed to be reliable as reported in the literature. The following heats of formation were determined: (COOH)2(a), -198.1±0.1; (COOH)2(ß), -197.8±0.1; UAW,, -328.7±0.4; Na2C204 -316.2±0.1; K2C204, -321.9±0.2; and K2C204-H20, -393.5±0.2 kcal/mole. The heat of the crystalline transformation (COOH)2(a) ? (COOH)2(ß) was determined to be 0.30±0.02 kcal/mole at 298.15° K.

Jan 1, 1970

By Raymond W. Hiteshue, Sam Friedman, Robert Madden

Experiments were made in a semicontinuous unit to provide engineering data for designing experimental continuous systems . These systems would be used to study the hydrogasification of hvab coal and char (from lowtemperature carbonization ) to high - Btu gas . In experiments at 800 ° C and with a coal residence time of several seconds , yields of hydrocarbon gases increased from about 2,000 scf / ton of maf coal at 250 psig to 7,000 scf at 1,000 psig . With 15 minutes residence time , yields increased from 8,000 scf/ton of maf coal at 250 psig to 17,500 cubic feet at 1,000 psig . In all cases , small quantities of heavy oils were produced along with the gaseous hydrocarbons . Production of oils could be minimized with a corresponding increase in gaseous hydrocarbons by increasing the retention time of the volatiles within the hot zone . Yields of gaseous hydrocarbons from char were slightly greater than from coal under similar conditions . Although the hydrogasification reaction is very pressure dependent , substantial quantities of coal (40 to 60 percent ) could be reacted to gaseous hydrocarbons at pressures as low as 50 psig provided reaction temperatures were increased to 1,200 ° C. It was also demonstrated that a hvab coal could be hydrogasified continuously without incurring agglomeration . This was achieved by dispersing coal in a relatively large reactor with concurrent flow of hydrogen . At 1,000 psig and 800 ° C , it was possible to react about 35 percent of the coal and to produce a gas containing up to 52 percent methane .

Jan 1, 1964

By Robert E. Wood

The temperature dependency of the low-density viscosity coefficients, ?°T, of helium and of nitrogen, 100° to 1,000° K, is correlated with empirical equations, and the temperature and composition dependencies of the low-density viscosity coefficients, ?°T, of helium-nitrogen mixtures are correlated with the Chapman-Enskog expressions by using the Lennard-Jones (6:12) potential function. The residual viscosity, ?T,P - ?°T (the difference between the viscosity of a compressed gas and the dilute gas at a given temperature), was found to be a function of the thermal pressure coefficient, (?P/?T)V, and two parameters, a and 1, which are characteristic of gas composition. The equation ?T, P = ?°T + a [(?P/?T)V]ß represented 1,340 higher pressure experimental viscosity values with a mean absolute deviation of 0.86 percent, and this equation was used to compute viscosities of the gaseous helium-nitrogen system for a range of temperatures and pressures including those encountered in Bureau of Mines helium purification processes and in a crude-helium conservation gas reservoir. Tabular viscosities for helium, nitrogen, and 13 helium-nitrogen mixtures are presented for 110 temperatures, 133° to 740&apos; K, and 49 pressures in the range 1 to 240 atmospheres. The accuracy of the tabulated viscosities varies because correlation parameters were obtained from experimental data of unequal reliability. It is estimated that uncertainties in the computed viscosity values are ±5 percent for the region 325° to 740° K, ±2 percent for the region 183° to 325° K, and ±5 percent for temperatures below 183° K. The latter uncertainty may rise to y10 percent as critical conditions are approached.

Jan 1, 1970

By L. B. Pankratz

High-temperature heat-content values of pure lutetium sesquioxide and dysprosium sesquioxide were measured over the temperature range from 298° to 1,800° K. Similar data for cerium sesquioxide were calculated from measurements of a mixture of cerium sesquioxide and dioxide and known values for cerium dioxide. The results for lutetium sesquioxide are regular. Dysprosium sesquioxide has a minor thermal anomaly near 1,590° K, the extra heat absorption being 220 cal/mole, Hexagonal cerium sesquioxide undergoes a transformation around 1,050° K, which is only slowly reversible; consequently results were obtained for both the low- and high-temperature varieties. The original heat-content data are reported, and smooth values of heat content and the corresponding entropy increments are tabulated. Equations were derived to represent the heat-content values.

Jan 1, 1963

By G. H. Keith

The Bureau of Mines determined the mechanism(s) involved in observed anomalous changes in mechanical properties of vanadium-base alloys. Tensile properties of electrorefined and commercial-purity vanadium-base alloys containing up to 5 atomic percent molybdenum or titanium were measured between 77° and 673° K. Snoek oxygen and nitrogen peak heights were measured to determine the changes in dissolved interstitial content caused by increasing quantities of solute. In addition, changes in lattice parameter were followed wit: precision X-ray techniques. Softening, observed in alloys containing titanium, is explained by the formation of a second-phase titanium compound with oxygen or nitrogen. However, because of partitioning of titanium between compound formation and solid solution formation, about five times the stoichiometric amount was required for complete reaction. Addition of 1 percent titanium drastically lowered the strengthening due to strain aging, at 673° K, and 2 percent titanium essentially eliminated it. All alloys were ductile at 77° K. Variations in the tensile properties of the molybdenum-containing alloys are explained by variations in the amounts of interstitial impurities present. The molybdenum did not react with these impurities and had no effect on strengthening due to strain aging. Commercial-purity vanadium alloys containing more than 2 percent molybdenum were brittle at 77° K.

Jan 1, 1969