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By R. F. Abernethy

A chemical method of determining microgram quantities of arsenic in coal was investigated by the Bureau of Mines to supplement a semiquantitative spectrographic method of determining arsenic in coal ash. In accordance with a method recommended by the International Organization for Standardization, 1-gram samples of coal are decomposed by wet oxidation with boiling sulfuric acid (H2S04) and nitric acid (HN03) to remove the organic matter. After heating to fumes of SO3 to remove HN03, the arsenic is separated as arsine by the action of zinc in H2S04 solution. The arsine is absorbed in dilute iodine solution in which the arsenic is determined colorimetrically by the molybdenum-blue reaction. Two modifications of the method for obtaining the arsenic in solution, in addition to the wet oxidation method, give satisfactory results. The modifications are (1) furnace ashing with MgO added to the coal, followed by treatment with H2S04, and (2) extraction of arsenic from the coal by dilute HNO3 without ashing. Float-and sink-tests show that arsenic is associated mainly with mineral matter in the three coals examined. High-temperature ashing tests show that very little arsenic is volatilized from coal ash below 1,000° C, but it is virtually all removed from the ash at 1,300° C.

Jan 1, 1968

By F. P. Haver

The Bureau of Mines developed a process to extract about 90 percent of the sulfur from molybdenite flotation concentrate by compacting the concentrate with one-quarter of its weight of aluminum powder, heating it at 800° C for 30 minutes, and then allowing the product to react with water. This thermite reduction yields an impure molybdenum alloy plus aluminum sulfide. The latter readily hydrolyzes, to yield pure hydrogen sulfide which can be converted to elemental sulfur by the Claus process. At least 95 percent of the molybdenum can be subsequently recovered as 99.95-percent-pure molybdic oxide.

Jan 1, 1968

By D. R. Forshey

The recent occurrence of fatal accidents in copper mines, presumably due to premature ignition of loaded holes by the heat from reacting ammonium nitrate-fuel oil (AN-FO) and pyrite-bearing ores, has led to an examination of this reaction. The reactivity of prilled AN-FO mixtures with pyrite-bearing ores and the effects of water, dilute sulfuric acid, and potential inhibitors on reactivity of the mixtures were evaluated. Initiation of an exothermic reaction was observed as low as 150° F with acid in the absence of inhibitors. Low concentrations of urea, calcium carbonate, zinc oxide, and magnesium oxide were effective in inhibiting the reactivity of the mixtures. The temperatures produced during the reaction of mixtures of AN-FO and pyrite-bearing ores, in the absence of inhibitors, always exceeded the temperature at which electric blasting caps are thermally initiated.

Jan 1, 1968

By E. A. Mihok

A pilot plant for treating mine drainage by neutralization with limestone was designed, fabricated, and operated by the Bureau of Mines. The process consists of (1) producing a very fine (minus 400-mesh) limestone slurry, (2) mixing the slurry with the mine water, (3) aerating the resulting mixture to remove carbon dioxide and precipitate iron, and (4) separating the solids from the liquid by sedimentation. A mine discharge of pH 2.8, containing 1,700 ppm total acidity, 36 ppm ferrous iron, and 360 ppm total iron, was treated at rates from 300 to 400 gpm. The treated water ultimately reached a pH of 7.4 and contained no detectable iron. The resulting sludge compacted to approximately one-third the volume of sludge from mine water neutralized with lime. The advantages of the limestone process, compared with the conventional lime process are as follows: Widespread distribution and lower cost of run-of-mine, indigenous limestone; simplicity of plant design; reduced hazards and plant operating and maintenance costs accruing from the use of a less reactive chemical agent; higher solids concentration of the precipitated sludge; and no deleterious effect caused by accidental overtreatment. While total process costs could not be determined, it is conservatively estimated that the cost of treating mine water by the limestone process is one-third to one-half the cost of the lime process, depending on the characteristics of the water to be treated and the availability and quality of limestone used.

Jan 1, 1968

By E. J. Kloos

Two self-contained breathing apparatus of the closed-circuit compressed-oxygen type were evaluated for performance at 32° to -25° F. Low-temperature effects of oxygen and carbon dioxide concentration, visual properties of the facepiece, and mechanical operation of the apparatus were studied. Although operation varied with the wearer, his breathing rate, the apparatus precooling time, and the temperature, results suggest that general use of currently approved compressed-oxygen closed-circuit breathing apparatus be limited to temperatures above 32° F.

Jan 1, 1968

By Joseph W. Martin

The Bureau of Mines investigated the backscattering of low-energy gamma rays as a method for rapidly determining the incombustible content of coal mine dust. In this method, 60-kev gamma rays from americium-24l penetrate the dust and are reflected by elements in the dust to a thin crystal scintillation detector. The number of backscattered gamma rays is proportional to the incombustible content. Tests of 40 dry, mine-dust samples containing 50 to 100 percent inert material show an average error of 2 percent. Calibration of the apparatus is necessary for each rock dust to account for variable composition. Results for samples containing more than 6 percent moisture are subject to error, but the values are lower than values obtained by chemical analysis, and thus fall on the safe side. Development of a small portable meter based on the backscatter principle appears feasible. Such a meter would find application within coal mines to check the effectiveness of rock dusting procedures.

Jan 1, 1968

By Robert L. de Beauchamp

The Bureau of Mines designed a chlorination apparatus to prepare CrCl2 free of CrCl3 by the direct reaction of chlorine and chromium. Equipment and procedures were developed for routine preparation of 25-pound batch quantities of anhydrous CrCl2. Calcium, iron, nickel, and silicon impurities were in the 0.01 to 0.05 percent range, and all other impurities were below 0.01 percent.

Jan 1, 1968

By R. W. Van Dolah

The feasibility of formulating cap-sensitive slurry explosives for use in underground mines with potentially flammable gas atmospheres was examined. Formulations containing aluminum metal as sensitizer and sodium chloride to reduce incendivity were prepared; some were cap-sensitive and had adequate air-gap. Flaked aluminum metal rather than the atomized type proved to be the more effective sensitizing agent of the formulations tested for incendivity in the large gallery of the Bureau of Mines, some were found to be suitably nonincendive.

Jan 1, 1968

By D. S. Burgess

The characteristics of gas-phase detonations were observed in 20 instrumented firings within earthen tunnels, in 100 such detonations in a 24-in-diam by l63-ft-long steel pipe, and in about 200 smaller scale firings. Most of the fuels studied were representative hydrocarbons--acetylene, propane, gasoline, and a roughly equimolar mixture of methylacetylene, propadiene, and propane. In a pipe with two closed ends, the detonable limits were demonstrated to be very nearly the same as reported limits of flammability. The side-on impulses (pressures integrated over 200-msec intervals) were shown to be the same function of concentration regardless of whether deflagration or detonation had occurred. In a pipe with only the initiation end closed, the impulses of all fuel-air systems tended toward the same level when averaged over comparable ranges of fuel concentration; the lower pressures with saturated hydrocarbons were nearly compensated by longer durations of pressure transient. In all fuel-air systems, unexpectedly high impulses were obtained with slightly lean mixtures. In earthen confining structures, the impulse, of the explosion was efficiently converted into momentum of the failing wall. In the configurations studied, an earth velocity of about 20 fps was critical to overcome the soil's resistance to shear. The destructive effect was determined by gas pressure rather than by total energy release. The assignment of a "TNT equivalent" to an explosive gas mixture is discussed in terms of the confinement of the mixture.

Jan 1, 1968

By Frank G. Schwartz

The Bureau of Mines developed a rapid test method for predicting the stability of motor gasoline during long-term storage. The amounts of gum and inorganic residue formed in 13 gasolines during a l6-hour oven test at 200° F were compared with the amounts formed in the same gasolines stored at 110° F, and analyzed following 8-, 16-, 32-, 44-, and 52-week storage periods. Satisfactory methods were developed for predicting gum and inorganic residue formation during fuel storage periods as long as 32 weeks at 110° F, the approximate equivalent of 5.7 years at 80° F. The only data required to apply the methods are the amount of gum and inorganic residue formed, and the amount of oxygen that reacted, during a l6-hour oven test. A direct relationship existed between inorganic residue formed during the oven test and during 110° F storage. Statistical treatment of the data showed predicted values were as reliable as determined values. By use of a modified Arrhenius equation, the 110° F storage time can be extrapolated to equivalent time at any temperature below 110° F. Thus by combining the stability prediction method with the mathematical extrapolation, the storage performance of motor gasoline for extended periods can be estimated at any temperature up to 110° F.

Jan 1, 1968

By David E. Nicholson

The Bureau of Mines has constructed a special compression chamber for developing stress-strain relationships of mine backfill and simulating the high compressive ground pressures encountered in underground mines. A one-dimensional, or Earth-Pressure-at-Rest model is proposed for backfills subjected to these pressures. Results of the compression tests performed in the chamber indicate that reliable stress-strain relationships can be developed from these tests. The primary objective of the test series was to evaluate the effectiveness of compaction of common backfills in retarding ground closure. Analysis of the stress-strain data shows an eightfold reduction in relative strain in optimum well-graded, compacted backfills over poorly graded, loose backfill material. Analysis of the one-dimensional compression test data also indicates a significant retardation of transmitted stress in dense compacted samples of backfill and natural sands. Although not fully understood, a deformation mechanism is thought to occur at the intergranular contacts in cyclic fashion causing frictional heat loss and a reduction in transmitted stresses in the densely packed materials. The experimental values of transmitted stress are compared with theoretical values of effective stress calculated from the one-dimensional compression relationships developed by Hendron (4).3 These experimental values of transmitted stress compare very closely with the theoretical values of effective stress.

Jan 1, 1968

By H. V. Makar

Laboratory tests were performed to obtain a quantitative description of the effectiveness of sodium sulfate (Na2SO4) for removing copper from molten iron and to determine the effectiveness of Na2SO4 on actual auto scrap. The tests were conducted on induction melted heats of iron averaging 0.58 and 1.50 percent initial copper and on cupola-melted auto scrap containing 0.45 percent initial copper. The Na2SO4 was added in powder form in amounts ranging from 2.9 to 43.8 percent of the weight of iron being treated. The data showed that copper removal for the various Na2SO4 treatments followed a similar trend, regardless of the iron composition that was tested. The equation Y = 1 - e-3.23x approximately reflects the relationship between copper removal and amount of Na2SO4 added, where Y is the fraction of copper removed and x is the ratio of the weight of Na2SO4 added to the weight of metal treated. Copper removals ranged from 3.3 to 74.5 percent and reductions down to less than 0.10 percent final copper were achieved in the auto scrap. Copper removals were generally accompanied by sulfur removal, and initial sulfur contents ranging from 0.10 to 0.20 percent were reduced to as low as 0.02 percent. High temperatures and long slag reaction times tended to induce copper and sulfur reversion from the slag, but, generally, the Na2SO4 treat¬ments were effective up to approximately 2,820° F with reaction times not exceeding 7 minutes.

Jan 1, 1968

By L. B. Pankratz

Heat contents were measured for Na2CaSi04 and Na2Ca2S02 between 298° and 1,300° K, for Na2Ca2Si309 between 298° and 1,500° K, and for Na4CaSi3O9 between 298° and 1,350° K. Copper-block drop calorimetry was employed. Reversible, first-order transitions were found for Na2CaSi04 and Na2Ca2Si309. The transition for Na2CaSi04 is at 830° K with a heat absorption of 160 cal/mole; that for Na2CagSi309 occurs at 750° K with a heat absorption of 1,550 cal/mole. Results for the other two silicates showed no irregularities. A table of heat content and entropy increments above 298.15° K and heat con-tent equations are included for use in thermodynamic calculations.

Jan 1, 1968

By R. H. Oitto

To determine whether reflectors could substitute for the trip lights referred to in the Federal Mine Safety Code, the Bureau of Mines studied trip safety devices under simulated haulageway conditions. The noticeability of reflectors compared with trip lights and fluorescent panels was evaluated from distances of up to 850 feet with light source intensities of up to 1-6 foot-candles (ft c). Reflectors tested consisted of a reflective lens in a holder secured to a frame that can be attached to a trip. Reflectors were found to be suitable for use as a trip safety device. In fact, for the conditions in many underground haulageways some reflectors would be more effective than a permissible trip light.

Jan 1, 1968

By Philip G. Freeman

The growth-promoting properties of coal-derived humus were tested by a variety of bioassay methods. Humate materials used included leonardite, a form of naturally oxidized lignite, and humic acids extracted from leonardite. It was found that the greatest effects were evident when water-soluble humic acid was applied to excised root tips. No significant short-term effect was noted when water-soluble humic acid was applied to stem or coleoptile sections. Root initiation was promoted in bean stems when high concentrations of coal-derived humate were applied. Gross weight of tomato plants was increased by up to 40 percent when coal-derived humates were added in concentrations of 101 to 104 ppm to the nutrient in a hydroponic growth test of 6 weeks' duration. It is concluded that coal-derived humate promotes the uptake of minerals, specifically iron, by serving as a metal chelate.

Jan 1, 1968

By C. B. Kenahan

The Bureau of Mines is developing methods for reclaiming the metal and mineral values contained in municipal incinerator residues. This report describes the first phase of the research, in which reliable methods for sampling and analyzing municipal residues were established and the composition and characteristics of the residues were determined. Samples were obtained from a variety of grate-type furnaces and also from a rotary kiln furnace. The samples were processed on a batch basis and separated into their natural categories by a variety of methods including screening, magnetic separation, air separation techniques, and handpicking. The main components of the residues were determined to be metal and metal oxides, glass, and ash.

Jan 1, 1968

By J. W. Town

The Bureau of Mines determined the physical properties of southeastern Idaho phosphate fines as related to mineral composition, particle size and liberation, beneficiation, and potential use in structural clay products. The phosphate mineral in the fines was identified by unit-cell dimensions to be essentially the same as the phosphate mineral fluorapatite identified in the coarser sizes. The mean particle frequency as determined by electron-microscopy and pipet-analyses was between 0.5 and 0.2 micron. Liberation of the phosphate could not be definitely determined because of the weathered condition of the minerals and their extreme fineness. No beneficiation scheme was developed that would concentrate the phosphate into a marketable fertilizer product; therefore, forming and firing tests were made to demonstrate that the fines can be used to manufacture structural clay products.

Jan 1, 1968

By James H. Aase

Selected glacial lake clay deposits in Minnesota were sampled, tested, and evaluated to determine their suitability for use as a bonding agent in iron ore pellet manufacturing. Preliminary tests conducted on clay samples obtained from five ancient glacial lake basins identified the clays in the Lake Agassiz glacial lake basin near Cook, Minn., as having the greatest bonding potential. An auger drilling program was conducted to obtain substantial quantities of representative material for detailed testing. The drilling indicated the presence of large clay reserves in excess of 500 million tons within the 12-square-mile area investigated. Bench scale tests indicated that the bonding properties of Cook area clays, when activated with relatively small quantities of sodium carbonate monohydrate (Na2C03?H2O), imparted excellent strength characteristics to iron ore pellets. Larger scale continuous pelletizing tests were made to confirm the bench scale results. These tests indicated that use of 1 percent activated clay alone as binder gave the iron ore pellets an overall strength slightly lower than with 0.75 percent bentonite, considered the industry standard. Use of 0.5 percent activated clay plus 0.5 percent bentonite produced better pellet strength qualities than use of 0.75 percent bentonite alone, without increasing the silica plus alumina content. The data from both bench scale and larger scale continuous tests suggest that the Cook, Minn., clays can be utilized after activation either alone or in combination with bentonite at an economic advantage over present pelletizing practice with bentonite.

Jan 1, 1968

By John Nagy

Dust explosion data obtained in laboratory tests by the Bureau of Mines are presented for 181 miscellaneous materials that present an explosion hazard. Data are given also for 50 dusts that present primarily a fire hazard and for 88 dusts that did not present an explosion hazard.

Jan 1, 1968

By Sam Friedman

The Bureau of Mines conducted experiments using bench-scale apparatus to explore the effect of large changes in process variables on the yield and composition of the gases produced by passing 800° C steam through a fixed bed of Pittsburgh seam (hvab) coal. The total yield of combustible gases increased throughout the given range for the following variables: Superficial steam velocity increasing from 0.02 to 0.12 fps, pressure increasing from 1,000 to 6,000 psig, residence time increasing from 0 to 60 minutes, and temperature increasing from 800° to 900° C; however, a greater increase in the yield of hydrogen in comparison with the increase in yield of methane reduced the gross heating value of the gas to around 470 Btu per scf at conditions giving the maximum yield. Pressures of 1,000, 3,000, and 6,000 psig at 0.09 fps steam velocity, 800° C, and 60 minutes residence time, respectively, produced methane yields of 20, 24, and 22 percent, based on maf coal, with the gross heating value of the CO2-free gas decreasing from 552 to 520 and to 470 Btu per scf. Methane concentrations in the CO2-free gas were 26, 22, and 14 percent, respectively. Based on the gross heating value of the coal, the percentage of the heating value recovered in the gas was 60, 71, and 87 percent, respectively. The use of tungsten sulfide as a catalyst for converting carbon oxides and hydrogen into methane was explored briefly using both a sulfur-free gas rich in methane and a sulfur-bearing synthesis gas (3H2:1CO).

Jan 1, 1968