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By T. E. Gray

This report describes the preparation characteristics of the significant coalbeds in Harrison County, W. Va. It is one in a series of Federal Bureau of Mines reports planned to determine coals suitable for the production of metallurgical coke, either as mined or after beneficiation. Over 6.5 million tons of coal was produced in Harrison County, W. Va., in 1958, of which over 3.7 million tons was cleaned mechanically in seven preparation plants. All of the coal cleaned was from the Pittsburgh bed. It has been estimated that more than 1,816 million tons of coal remains in the county in beds 12 inches or more thick. The Pittsburgh and Redstone beds were selected by the Bureau for a study based on current production rates and estimated minable reserves. Sample locations were selected following a study of the literature, conferences with mining engineers and mining company officials in the field, and examination of the available sites. Six samples were collected from the Pittsburgh bed, and three samples came from the Redstone bed, Float-and-sink tests of the samples collected from the Pittsburgh and Redstone beds showed that neither coal could be upgraded to a metallurgical fuel under the standards set up for this study, even after intensive preparation. Finer crushing of the samples moderately increased the yields and slightly reduced both the ash and the sulfur contents in the 1.30-specific-gravity float fractions. Finer crushing slightly decreased the yields in the 1.58-specific-gravity float fractions, whereas it reduced the sulfur content 0.11 percent for the Redstone sample and 0.46 for the Pittsburgh sample.

Jan 1, 1961

By A. Gene Collins

Rapid, sensitive, and precise methods of determing major, minor and trace constituents of oilfield brines are needed. Several methods have been developed or adapted by the Federal Bureau of Mines at the Petroleum Research Center, Bartlesville, Okla. The following methods are described in this report: Spectrophotometric and volumetric for iodides and bromides; potentiometric for pH, alkalinity, acidity, borate boron, total boron, and organic boron; gravimetric for potassium; disodium ethylenediaminetetraacetate (EDTA) volumetric for total hardness, calcium, and magnesium; spectrophotometric for fluorides; and color comparison .for arsenic. Adequate sensitivity, precision, and accuracy were obtained for each method. The Bureau of Mines pioneered in research on the analysis of oilfield waters (2, 46, 47).6 However, several of these early procedures were quite time consuming. Also, they did not include methods for determining trace and minor constituents of brines.

Jan 1, 1961

By Robert K. Koch

The reactions of alumina and alumina monohydrate with wet hydrogen fluoride gas were studied by the Federal Bureau of Mines to determine the feasibility of producing commercial-grade aluminum fluoride from offgases generated by pyrohydrolysis of siliceous fluorspars. The test results showed than an aluminum fluoride reactor operating at maximum efficiency could retain 96 percent of the fluorine contained in off-gases generated by pyrohydrolysis of siliceous fluorspar. The requirements are a reactor temperature of 200° C. and a reactor entrance gas containing 5 mole-percent hydrogen fluoride. Partial pressure equilibrium constants were determined for the reaction of alumina monohydrate and wet hydrogen fluoride gas from 200° to 350° C. and for the reaction of alumina and wet hydrogen fluoride gas from 350° to 700° C. Both reactions are reversible, and they proceed in directions that are dependent upon the temperature and the relative HF:H2O concentration. Logarithms of the equilibrium constants were used to plot the reaction isobars; these can be used to calculate the theoretical maximum efficiency of a reactor processing wet hydrogen fluoride gas between 200° and 700° C. The theoretical maximum efficiency decreases with increasing temperature.

Jan 1, 1961

By Perry D. Teitelbaum

In two earlier studies the Federal Bureau of Mines undertook to explore comprehensively the dimensions of the Nation's energy balance. The first of these studies, published in 1950 as Bureau of Mines Information Circular 7582, by Harold J, Barnett, was primarily concerned with projections of future domestic energy requirements and supplies, because these related to projected growth in major fuel-consuming sectors of the economy, changing rates of energy-use efficiency, and interfuel substitution patterns. But, to provide the essential background for these projections, it was first necessary to assemble and examine in some detail the quantitative information on the size and shape of the current United States fuel economy. Among other things, Barnett's path-breaking study indicated the need to consider energy as an entity, particularly for public and private policy makers, industry and commodity analysts, economists, and others concerned with long range questions of domestic and international energy supply and demand. The study also spotlighted a gap in the fabric of current economic intelligence; no comprehensive collation and reconcilation in any single report of available published statistical information covering the origin -a disposition of all energy materials existed. In response to this latter need, the Bureau of Mines prepared the second of the two studies referred t3 above. This was published in 1951 as Report of Investigations 4805, by W, H, Lyon and D, S. Colby, and it consisted of statistical information on the production and use of each of the various fuels and electric energy in the United States for 1929, 1939, and 1947; all were presented in tabular form and on a uniform basis. The three years selected were chosen largely on the basis of data availability.

Jan 1, 1961

By C. F. Ellis

Interest in the composition of automobile exhaust gases has been greatly accelerated by recent studies that have indicated that these gases contribute to smog formation in urban areas. Several analytical methods have been published for the analysis of the hydrocarbons in the exhaust gases, but similar information has not been published on the analysis of the oxygenated compounds. This report presents procedures for chemical analyses of certain oxygenated compounds, procedures for sampling the exhaust gases for these analyses, and the analytical results of some experimental work in which these procedures were used. A stationary 1956 model, 170 horsepower, V-8, dynamometer-mounted engine, operated to simulate vehicular cruise conditions, was used for the study. Exhaust gases produced from a regular-grade Midcontinent gasoline during 15-40- , and 60-mile-per-hour cruise operations were analyzed by chemical methods for formaldehyde, total aldehydes, total carbonyls, total alcohols, carbon associated with the oxygenated compounds, and the oxides of nitrogen. Experimental results indicate: 1. The range of concentrations of the total of the functional groups of oxygenated compounds, expressed as moles per million moles of water-free exhaust gases, is about 90-100; the concentrations increase with engine speed. 2. Aldehydes comprise about 80-90 mole- percent of the total of the oxygenated groups, and formaldehyde accounts for about 50 mole-percent of the total aldehydes. 3. The order of magnitude of the concentration of the carbonyls is the same as that for the aldehydes, indicating that ketones are not a major group. A colorimetric test indicates that methyl ketones Constitute about 2 mole-percent of the oxygenated compounds.

Jan 1, 1961

By Lowell Stroud

Since 1929, the Helium Activity of the Bureau of Mines has operated a helium-extraction plant at Amarillo, Tex. The natural gas that supplies this plant is obtained from the Cliffside geologic structure 12 miles to the northwest and over the years, has become known simply as "Cliffside gas," There is need for published data on the low-temperature phase equilibria of helium-bearing natural gases. To date, little information has been published on the equilibrium phase compositions, solution of helium in condensed natural gas, condensation characteristics, or equilibrium vaporization coefficients for methane, nitrogen, and helium in helium-containing systems. A windowed phase equilibrium apparatus (8)6 was used to obtain 105 equilibrium samples, representing 35 experimental conditions of condensed Cliffside gas at pressures of 100, 200, 300, 400, and 500 p.s.i.a. and temperatures from 0° to -270° F. Data on equilibrium vapor-liquid composition for Cliffside gas are presented in both tabular and graphic form and are discussed in detail to show their relationship to certain criteria that must be met to effect an efficient separation of helium from natural gas by means of low-temperature processes. Facts about condensation characteristics and solution of helium in the liquid phases are included, The important relationship of these two factors in decreasing the percentage of total helium lost by solution in the liquid phase is discussed.

Jan 1, 1961

By R. Barany

Thermodynamic calculations pertaining to the minerals gibbsite, kaolinite, halloysite, and dickite have been hampered by the lack of adequate heat and free energy of formation data. Previous data for gibbsite were highly uncertain, and there were no data for the other three substances. By use of hydrofluoric acid solution calorimetry, the Bureau of Mines derived heat of formation values from the elements and from the oxides for the four substances, and the data were combined with known entropy values to obtain the corresponding free energies of formation. The results show that gibbsite and halloysite are thermodynamically unstable with respect to the oxides (a- alumina, a- quartz, and liquid water) at 298.15° K,, while kaolinite and dickite are only moderately stable (to about the same degree), The instability of halloysite, in comparison with kaolinite and dickite, results in a 60°-lower equilibrium decomposition temperature.

Jan 1, 1961

By P. M. Sullivan

The principles and application of amalgam electrolysis to the recovery of zinc and tin from secondary products were studied; this Bureau of Mines project was one phase of investigating the development of more efficient methods for processing iron-bearing zinc and tin to produce both base metals of high purity. Zinc of 99-99-percent purity was recovered from galvanizer's dross with recovery efficiency of 98 percent. Tin of 99.9-to 99.99-percent purity was recovered from hardhead with recovery efficiency of 81 percent. Both materials were treated by the same method in separate systems. Mercury was used to leach zinc from dross and tin from hardhead to form amalgams of each metal, both of which were subsequently refined electrolytically to produce high-purity metal. Impurities that were contained in both secondary products behaved as theoretically predicted; impurities that were insoluble in mercury remained as sludge in the leaching column. Except for lead, the readily amalgamated impurities were prevented from fouling the electrolyte by the blocking action of the amalgam electrode. Lead impurity in the tin-refining system dissolved and immediately precipitated as the sulfate. The primary advantage of the amalgam refining method lies in direct recovery of the extremely pure base metal from highly contaminated secondary material.

Jan 1, 1961

By Donald F. Smith

This report describes the construction and calibration of two ice calorimeters and includes results of high-temperature heat-content measurements, made by the Federal Bureau of Mines, on rubidium fluoride, hafnium tetrafluoride, cesium chloride, and cesium iodide. The heats and entropies of fusion of rubidium fluoride, cesium chloride, and cesium iodide have been calculated at their respective melting points using equations derived from the experimental heat-content data. Hafnium tetrafluoride did not melt within the range of temperatures investigated. Heat and entropy of transition of cesium chloride from the alpha to the beta form were also determined. INTRODUCTION Free-energy data usually afford the cheapest and quickest means of determining the feasibility of experimentally untested reactions. For known reactions, free-energy data show the variation of the equilibrium constant with temperature and make it possible to calculate, without experiment, the maximum ratio of product to raw material for a given chemical process.

Jan 1, 1961

By M. E. Tyrrell

Despits its high melting point (2,135° C.), resistance to attack by molten metals, and its hardness (8), spinel (MgO?Al203) synthesized by the fusion of alumina (Al 2 0.) and magnesia (MgO) is not used on a large scale as a commercial furnace lining, mainly because of the prohibitive cost. This investigation by the Federal Bureau of Mines was prompted by the possibility of producing synthetic spinel from inexpensive raw materials by methods outlined in U.S. Patent 2,029,773, "Process for Obtaining Products Containing Spinets," dated February 4, 1936. In this patent Ture B. Haglund described a process for recovering crystalline spinels from melts in the system Mg0?Al203-2CaO-SiO2, a system well suited to the use of starting materials such as dolomite CaMg(C03)2, olivine [2(Mg?Fe)0.Si02], and bauxite (Al203?2H20) which are abundant in the southeastern United States. Compositions, ranging from a low content in the eutectic mixture of 35 percent spinal and 65 percent dicalcium silicate (2 CaO?SiO2) to a high of 75 percent spinel and 25 percent dicalcium silicate, were fused in electric furnaces of the arc-resistance and internal-resistance types. So long as members of the system were in proper chemical balance, "dusting" slags could be produced over the entire range of spinel concentration.

Jan 1, 1961

By W. L. Schmidt

The effect of a water-repellent film in sandstone cores on the effective permeability-saturation relationship was investigated as part of a cooperative research program between the Bureau of Mines and the American Gas Association. The repellent film was formed by the reaction of methyltrichlorosilane3 with the connate water in the core. Other researchers have reported on the use of silicone chemicals to alter the flow characteristics of porous media (1-3, 5-7, 9, 10).4 The previous studies, however, dealt almost entirely with oil-water or oil-gas systems and not with water-gas systems. The primary purpose of this study was to determine the feasibility of using silane to retard the influx of water into natural-gas storage wells and to determine the necessary requirements for achieving this result. The success or failure of silane treatment as a remedial measure depends on its effect on gas-production rate and attendant water production.

Jan 1, 1961

By K. K. Kershner

Nickel having a purity of more than 99.99 percent with reference to metallic impurities was electrodeposited at the Rolla Metallurgy Research Center of the Federal Bureau of Mines. The production of high-purity nickel is in keeping with the current trend in technologies for producing metals with lower and lower percentages of impurities. To understand more fully the role to be played by nickel by itself and as a component in many alloys, the element must be in a state of high purity. Procedures are outlined for purifying nickel solutions by precipitating and filtering off impurities. Details are given for using the purified solutions as electrolytes in depositing high-purity nickel. The elecneleposited nickel contained 0.0005 to 0.002 percent each of cobalt, copper, aid iron together with spectrographically detectable traces of aluminum, magnesium, and silicon. The deposits were smooth and dense; the crystalline structure was typical of an electrodeposited metal. Some preliminary experiments for purifying nickel solutions by liquid-liquid extraction are also described in this report. Tests of this type were limited since more encouraging results were obtained by other methods of purification.

Jan 1, 1961

By D. Bienstock

A high-B.t.u, gas can be synthesized by the catalytic methanation of a mixture of 2.5 to 3 parts of hydrogen to 1 part of carbon monoxide, obtained in the gasification of coal, using a steel catalyst followed by Raney nickel in a hot-gas-recycle system. Conversion of 99 percent of the H2+CO yields a fuel gas with a heating value of 983 to 1130 B.t.u. per cubic foot containing 78 to 96 percent methane, no carbon monoxide, and very small amounts of unsaturated hydrocarbons. With the steel catalyst alone, conversions were 85 to 90 percent, giving a fuel gas of 810 to 868 B.t.u, per cubic foot, or 847 to 975 B.t.u. on a C02-free basis. INTRODUCTION In 1948 the U.S, marketed production of natural gas was 5.15 trillion cubic feet; by 1958 it had reached 11.0 trillion cubic feet, a rate of growth of 8 percent annually. 4 5 Although demand is expected to increase less rapidly, by 1966 it may reach 16 trillion cubic feet, based on an estimated 4.7 percent annual increase.6

Jan 1, 1961

By L. R. Fisher

The purpose of this investigation was twofold: (1) To devise a rapid method for determining quantitatively the porphyrin-carboxylic acid content of a particular crude-oil porphyrin aggregate, and (2) to isolate porphyrins in the crystalline state from crude-oil porphyrin aggregates. The first purpose was accomplished by applying adsorption chromatography. In fulfillment of the second aim three different crystalline porphyries were isolated by methods which involved both adsorption chromatography and fractionation of benzene solutions with hydrochloric acid of varying strength. The three porphyrins had etio, rhodo-, and phyllo-type absorption spectra, respectively. INTRODUCTION Many samples of petroleum have, as interesting minor constituents, chemical compounds known as metalloporphyrins. Their presence in crude oil and other bituminous materials was first discovered by Treibs a quarter century ago. Much experimental work has been done on metalloporphyrins because of their importance to the petroleum industry. They have a deleterious effect on refining catalysts. The ash resulting from the burning of heavy fuel oil is very reactive, We to the presence of metallic constituents, particularly vanadium. In oil-fired gas turbines, the ash may build up on the blades, causing imbalance of the rotors and, in addition, severe corrosion. In industrial boilers, the ash residue is responsible for severe damage to boiler tubes and to the refractory brickwork (15).4 Through study of the chemical constitution of the various metalloporphyrins found in petroleum, much can be learned concerning the origin, migration, and history of crude oils.

Jan 1, 1961

By J. E. Miller

This paper reports experimental determinations by the Bureau of Mines of compressibility factors to 4,000 pounds per square inch absolute (p.s.i.a.) for helium at temperatures from -10° to 130° F. and for 16 helium-nitrogen mixtures at 70° F. This information is needed for computing accurate discharge volumes and is necessary for determining an average-density value for use in orifice-meter formulas. In thermodynamic calculations, several functions of the compressibility factor with pressure and temperature are required. The data in the original publications (6, 8)5 of this study have been reexamined and have been given a more comprehensive treatment. The recalculated compressibility factors are higher by approximately 0.2 percent because in the earlier work a linear relationship between the compressibility factor of helium and pressure was assumed.

Jan 1, 1961

By Donald W. Mitchell

Studies were made in the Bureau of Mines Experimental coal mine to evaluate the effectiveness of a few extinguishing agents and techniques for controlling a fire on a simulated mining machine. The investigation showed that water containing an alkali-metal salt or a surface-active (wetting) agent was more effective than water alone. For close attack, fog applications was the most effective technique studied; high rates of agent application controlled the fire more quickly than low rates. The ability to control the fire increased as the distance of attack decreased. Dry powders controlled the fire when applied by shovel but not when applied airborne by rock-dust distributor or by hand fire extinguishers. Dry alkali-metal salt powders (potassium and sodium bicarbonates and sodium tetraborate) quenched the fire more readily than limestone dust. In each instance the finer powder, the greater its effectiveness. In an open ventilated entry, smoke and hot gases backed against the air currents. An airspeed of 230 feet per minute was required to permit approach to within 10 feet of the fire. At lower airspeeds, approach could be made by extending the brattice across the bottom two-thirds of the entry, by pushing the smoke ahead with water sprays, or by discharging dust from a rock-dust distributor. In a dead-end entry, the fire was approached to within 30 feet by coursing fresh air along an airtight line brattice; however, it was safer, easier, and less time-consuming to attack the fire from a fresh-air base 100 feet away with a solid stream or by high-expansion foam; the latter method was more effective.

Jan 1, 1961

By Martin H. Stanczyk

The direct dissolution of a typical zinc sulfide flotation concentrate by elevated temperature and pressure leaching was investigated. The concentrate assayed about 55 percent Zn, 32 percent S, 6 percent Fe, and 1 percent Pb and contained minor quantities of copper and precious metals. The influence of various factors on the dissolution of the zinc in acidic and ammoniacal pulps when using oxygen as the oxidant was determined. The tests revealed that the sphalerite was difficult to oxidize. Complete dissolution of the mineral required vigorous and intimate nixing of the gaseous, liquid, and sold phases. The addition of pyrite or sulfuric acid to water slurries of the concentrate was required to obtain a high zinc extraction when leaching under acidic conditions. The quantity of pyrite and acid used was about 0.125 and 0.25 pound, respectively, per pound of zinc sulfide contained in the leach charge. In tests with acid, about 96 percent of the zinc was extracted from the concentrate in 1 hour at 200° C. when the oxygen partial pressure was 75 pounds per square inch gage or higher. Leaching with a continuous flow of air as the oxidant gave results that were almost as good as those obtained when oxygen was used, In tests with air fed through the autoclave at 320 liters per hour, 95 percent of the zinc was dissolved in 1 hour, Acid leach solutions assaying approximately 58 grams Zn per liter and containing Fe, Ni, Cr, and Cu impurities were produced in the better tests. The leached residue consisted essentially of red iron oxide together with substantially all of the lead and precious metals.

Jan 1, 1961

By Benjamin Petkof

Production quarry blasts in three rock types were photographed with a high-speed camera. Analysis of the films showed that step increases sometimes occur in the horizontal velocity of the broken rock. These step velocity increases were observed only in the first foot or so of rock movement. This observation indicates that the gaseous products of the explosion do additional work on the rock after it is crushed and cracked by the initial compressive-stress pulse and the reflected tensile-stress pulse. The observed initial fly-rock velocity is compared with the calculated fly-rock velocity for reflection spalling. A mechanism possibly causing the velocity increases is discussed. INTRODUCTION When a small concentrated charge of explosive is detonated at the bottom of a drill hole near a free surface, two modes of rock failure have been observed; both are associated with the stress pulse generated in the rock by the detonating explosive. The first mode of failure is the crushing and radial tensile cracking associated with the initial passage of the compressive-stress pulse as it propagates outward from the explosion. This type of rock failure is usually confined to the immediate vicinity of the charge hole. The second mode of failure is the tangential and radial tensile cracking associated with the tensile-stress pulse that is reflected from the free surface. This mode of failure is commonly called scabbing or spalling and has been shown to be a primary cause of rock failure in crater formation at one free surface. (3).4

Jan 1, 1961

By E. G. King

Sodium-aluminum and calcium-aluminum silicates are important rock-forming minerals. While many of them are of only theoretical interest, several are of practical importance--as ceramic raw materials and as potential future sources of aluminum. Heretofore, thermodynamic data for these minerals were incomplete; and in many instances missing data were difficult to estimate reliably. This has seriously hampered thermodynamic calculations pertaining both to the natural formations of these minerals and to their decomposition in sintering and fluxing reactions. This paper reports the results of the Federal Bureau of Mines measurements of low-temperature heat capacities of four crystalline silicate minerals--dehydrated analcite (NaAlSi2O6), hexagonal anorthite (CaA12 Si208), lawsonite (Ca2Al2Si2080?2H20), and leonhardite (Ca2Al4Si8C24?7H2O). It augments previous similar measurements of related minerals, which were summarized recently.4 The measured heat-capacity data were used to derive entropy values for the four minerals at 298.15° K. Some relations between these entropy values and those of other similar minerals were discussed. These relations illustrate the difficulty of estimating entropy values of tertiary (or higher) silicates.

Jan 1, 1961

By H. D. Hess

This report presents the results of laboratory mineral evaluations conducted by the federal Bureau of Mines under the joint sponsorship of the U.S. Atomic Energy Commission (AEC) and the Bureau a! Ships, U. S. Department of the Navy. The major purpose of this investigation was to examine and evaluate zirconium minerals representing sizeable deposits in an effort to locate com¬mercial sources of high-hafnium ores. Although determination of the hafnium content was the principal objective, each of the zirconium minerals also was analyzed for combined zirconium-hafnium oxide, silica, uranium, thorium, yttrium, and cerium. The general laboratory procedure involved microscopic examination of the test samples, concentration of the hafnium-bearing zirconium mineral by standard laboratory techniques, and analysis of the derived concentrate by quantitative microscopic, chemical, and X-ray spectrographic methods. Of the several hundred samples tested under this program, 147 are discussed in this report, including 94 from domestic occurrences and 53 from widespread foreign sources.

Jan 1, 1962