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By F. P. Haver

A method to recover copper and elemental sulfur from chalcopyrite concen¬trate, using a ferric chloride leach, CuFeS2 + 3FeCl3 ? CuCl + 4FeCl2 + 2S, was reported by the Federal Bureau of Mines in 1971 (Report of Investigations 7474). Since that time, additional work has been done to improve certain steps in the procedure; that is, the recovery of sulfur from the leach residue, the recovery of copper and iron from the leach solution, and the regeneration of the leach solution. It was determined that over 99 pct of the elemental sulfur in the leach residue could be extracted at ambient temperature with an ammonium sulfide solution. Heating the pregnant solution precipitated crystals of rhombic sulfur (99.5 pct purity) and liberated ammonia and hydrogen sulfide for recycle. Copper with a purity in excess of 99 pct was obtained from the leach solution by electrolysis, using a diaphragm cell, with an energy requirement of less than 0.7 kW-hr/lb. Metal was deposited as a weakly adherent powder that could be easily dislodged from the cathode and withdrawn continuously from the cell in the form of a slurry. During electrolysis, part of the Fe(II) was oxidized to Fe (III) at the anode so there was no chlorine evolution. The leach solution was regenerated by direct oxidation of the spent electrolyte with air or oxygen in a turboaerator at 80° C. This precipitated the iron dissolved during leaching in an easily filterable form, Fe203.xH20, and converted the remaining Fe(II) to Fe(III).

Jan 1, 1975

By Neil B. Young

Carbonate minerals constitute a major fraction of the oil shale in Colorado's Green River Formation. Quantification of carbonate minerals is important for the characterization of oil shale, particularly because of their thermal activity in production of oil from shale. The carbonate minerals found in this oil shale are nahcolite (NaHCO3), dawsonite [NaA1(OH)2CO3], dolomite [(Mg1-xFx)Ca(CO3)2], calcite (CaCO3), and ferroan [(Mg1-xFex)CO3]. Although carbonate minerals can be removed by acid extraction from the balance of the oil shale, direct determination of carbonate minerals is complicated by the occurrence of the same cations in more than one mineral. A method for assigning the acid-soluble cations to the individual carbonate minerals was developed from two assumptions based on oil shale geochemistry: (1) Calcite and ferroan do not occur together, and (2) the ratio of iron and magnesium is the same in dolomite and ferroan. These assumptions were tested by the Bureau of Mines by applying the technique for assigning cations to 219 samples from the saline section of the formation. The reported carbonate mineral amounts were compared statistically with X-ray diffraction peak heights, verifying the cation assignment method.

Jan 1, 1975

By M. C. Irani

The Bureau of Mines, in cooperation with the Mine Safety Appliances Co., has developed a new methane analyzer system for underground applications. Methane enters coal mine ventilation air from the breakup of coal at the active face, from the collapse of roof rock during retreat mining, and from the ribs abutting virgin coal. Each source contributes varying amounts to the total emission, depending upon rate of mining, type of mining, and the character of the coalbed and adjacent strata. The evaluation of individual parameters of methane emission requires the continuous monitoring of individual mine sections over a long period of time. The methane analyzer system was developed to meet this need. The system has been installed and operated in an active mine in the Pittsburgh coalbed. The system and details of its installation and calibration are described. Data are presented to substantiate its reliability.

Jan 1, 1975

By H. B. Carroll

The performance of commercially available portable instrumentation for detecting nitrogen dioxide, sulfur dioxide, and hydrogen sulfide was evaluated. Length-of-stain detector tubes from several manufacturers were included in the study. The instruments were evaluated in atmospheres with 50-and 80-percent relative humidities at 75° F and containing test gas concentrations of 0.1, 0.25, 0.50, 1.0, 1.5, and 2.0 times the threshold limit values. The results from the gas analyzers were correlated with the known contaminant concentration by calculating and plotting an estimated line of regression, confidence limits, and correlation coefficient for each detector system. An increase in the relative humidity from 50 to 80 percent at /5° F changed the instrument response to the contaminants. The uncertainties in detection precision reported are for the observer-instrument system. The main difference or inconsistency in toxic gas concentrations determined with length-of-stain tubes resulted from the observer's interpretation of the results rather than from a predominant difference in the tubes.

Jan 1, 1975

By Lawrence K. Barker

Crude shale oil produced by underground retorting of Green River Formation oil shale was hydrogasified over a cobalt-molybdate-on-alumina catalyst at operating temperatures ranging from 800° to 1,300° F, pressures of 500, 1,000, and 1,500 psig, and a liquid hourly space velocity of 1.02 volumes of oil per volume of catalyst per hour (Vo/Vc/hr). At a temperature of 1,300° F and pressure of 1,500 psig, 94 weight-percent of the liquid feed was converted to gas containing 72 volume-percent methane. With two reactors in series at a temperature of 1,170° F in reactor 1 and 1,260° F in reactor 2 and a pressure of 1,500 psig, 97 weight-percent of the liquid feed was converted to gas with a methane content of 75 volume-percent. Liquefied petroleum gas (LPG) was hydrogasified at operating temperatures ranging from 500° to 1,400° F at a pressure of 500 psig over a cobalt-molybdate-on-alumina catalyst. Similar experiments were made with an empty tubular reactor. The data indicate that gasification reactions in the presence of a cobalt-molybdate catalyst change from predominantly a catalytic (carbonium ion) reaction to predominantly a thermal (free radical) reaction at temperatures greater than 1,100° F. The data also indicate that a reaction temperature of 1,350° F is necessary at the space velocities used in this investigation to make a synthetic natural gas (methane content of 90 volume-percent) from in situ crude shale oil.

Jan 1, 1975

By B. W. Madsen

Research by the Bureau of Mines has shown that treatment of open pit waste by crushing and sizing followed by flotation of the fines and leaching the coarse fraction results in greater metal recoveries than obtained by leaching only. Tests with a chalcocite-bearing quartz monzonite mine waste sample that had been crushed to minus 6 inches and screened on 1/2 inch yielded copper and silver recoveries of 71 and 22 percent, respectively, by the combined flotation-leaching process, compared with 48 percent of the copper and no silver recovered leaching the run-of-mine material. Copper was more readily leached from the coarse material with the minus 1/2-inch fines removed than from material with the fines included. The improved leaching was attributed to improved permeability and the associated improved circulation of air to the interior of the ore column. Cost estimates showed that the proposed intensive treatment of mine waste will require a greater capital investment and higher annual operating costs than conventional milling and dump leaching process. However, the income from the additional metal production offsets the increase in capital investment and operating costs, resulting in additional profit.

Jan 1, 1975

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 Peter D. Lohn

The Bureau of Mines conducted both laboratory and field investigations to study the effectiveness of medium-pressure (up to 30,000 psi) water jets in controlling the generation of airborne respirable dust during the hydraulic fragmentation of coal. Laboratory studies were conducted at the Farmington High Energy Test Site of the Twin Cities Mining Research Center, and field studies were carried out at the Humphrey No. 7 mine, Mount Morris, Pa., in the Pittsburgh coalbed. The water jets were produced by commercially available triplex pumps. The dust samples were collected by midget impinger samplers, and analyzed by electronic and optical counting techniques. Respirable dust concentration for a full-scale production model was projected at below 2 mg/m3, the maximum exposure allowed by the Federal Coal Mine Health and Safety Act of 1969.

Jan 1, 1975

By Fred N. Kissell

Air recirculation caused by dust scrubbers at coal mine working faces was examined by the Federal Bureau of Mines with regard to the potential hazards caused by a possible buildup of methane gas. A theoretical analysis indicated that there was no apriori way to predict the effect of scrubber recirculation on methane concentration levels. Experiments conducted in a full-scale model of a working face area indicated that methane levels were dependent to a great extent on the location of the scrubber exhaust, but that the scrubber recirculation did not substantially increase the methane concentration above those levels that would have prevailed were the scrubber not in operation. An analysis of two underground scrubber trials showed that the scrubbers had no significant effect on methane levels, and a review of explosions attributed to recirculation showed that these were characterized by a lack of fresh air as well as recirculation. It was concluded that high methane levels are due more to a lack of fresh air than to recirculation.

Jan 1, 1975

By W. E. Robinson

Differences in the composition or chemical structure of the organic material in samples of Uinta Basin (Utah) oil shale were studied relative to stratigraphic position within the Green River Formation. This involved a systematic study of the soluble organic material and the insoluble organic material (kerogen) present in the samples. Emphasis was placed upon the distribution of the alkanes (normal and isoprenoid compounds) in the soluble extracts and upon the aromaticity of the kerogen. Significant differences exist in the chemical composition of the organic material from various strata within the Uinta Basin, some of which were related to burial depth but most were related to source material variations, environmental differences, or other factors. The Uinta Basin samples differed significantly from Piceance Creek Basin and Green River Basin samples in the large amount of soluble extract they contained.

Jan 1, 1975

By John F. Papp

The Bureau of Mines has sampled microstructure of low-pressure flat flames by mass spectrometer for normal methane-oxygen-argon and for methane-oxygen-argon-bromotrifluoromethane flames. The physical and chemical phenomena, and the method of analysis of mole fraction data to evaluate net reaction rates are here considered in detail. Included is a computer program listing with output on one flame. Chemical species considered are CH4 , CO, CO2, H, H20, OH, Ar, H2, O2 , O, H2CO, CH3 , CF3Br, HF, HBr, Br, CH3Br, HCO, F2CO, CH2 CF2 , H02.

Jan 1, 1975

By Patrick J. Cain

The fatigue-failure characteristics under high-frequency (10 KHz) cyclic loading were determined for a marble, granite, and quartzite. The rock speci-mens were cyclicly loaded (using a high-power piezoelectric sonic transducer) at a constant strain amplitude generated by forming a longitudinal standing stress (strain) wave in the cylindrical test specimen. The number of load cycles required to fail each rock type at a given strain amplitude was deter-mined. The fatigue fractures were tensile in nature and the fracture load amplitudes were as low as 30 pct of the static tensile strength. Also the internal heating of the rock caused by the material damping (internal friction) was measured. The damping and internal heat generation in the specimens was analyzed to show that nearly all of the power input can be accounted for as a change in enthalpy in the specimen. Using these results the thermal strain in the rock was calculated to evaluate its contribution to fatigue failure. The thermal strain was found to range up to 30 pct of the dynamic strain amplitude depending on the load amplitude and the number of load cycles. The specific energy required for failure was determined and possible applications of the high-frequency fatigue fragmentation process are discussed.

Jan 1, 1975

By P. R. Tisot

The structural response of propped oil shale fractures was determined for each of two different grades of Green River oil shales (38.0 and 29.0 gpt) as they were heated in an inert atmosphere from ambient to subretorting temperatures (below those required for rapid pyrolysis of the organic matter). Small oil shale cores were propped apart by 3-mm glass beads to simulate a small cross section of a propped oil shale fracture between an injection and a producing well. These specimens were then heated at a uniform bate up to 800° F in a specially designed test cell under stress levels from 100 to 1,000 psi in biaxial and in triaxial confinement. Under the conditions of heat and compressive stress utilized in this study, all of the propped fractures in the two oil shales underwent structural deformation ranging from partial to complete collapse, as evidenced by proppant embedment. Structural collapse of induced fractures would in turn result in serious impairment or complete loss of the fracture flow capacities of the specimens. Results from this Bureau of Mines study indicate that underground retorting of Green River oil shale may be seriously impaired by loss of permeability when utilizing propped fractures in oil shales assaying more than 28 gpt.

Jan 1, 1975

By G. L. Gates

The waters used to waterflood the Wilmington oilfield were studied by the Bureau of Mines, in cooperation with the city of Long Beach, Calif. Increases in the pressure of the injection wells indicated that they were being plugged by materials suspended in the waters. This study was made to identify the suspended materials, determine their origin, and find methods of preventing their formation. The suspended oil-coated materials were iron sulfide, barium sulfate, calcium carbonate, clay, and sand (or silica). Results indicated that the sulfide, which was as high as 90 milligrams per liter, was the product of sulfate-reducing bacteria. The injection of ocean water increased the sulfate content of the waters in the petroleum reservoirs from 3 to 250 milligrams per liter, thereby furnishing sulfate for growth of the bacteria. The waters were supersaturated with barium sulfate. Laboratory tests showed that sulfide could be removed from the waters by adding iron at a cost of 1 to 2 mills per barrel. The solubility of iron sulfide and calcium orthophosphate in the injection waters was also determined.

Jan 1, 1975

By Richard J. Leary

The inputs of capital and labor to support future iron ore production were developed by the Bureau of Mines from projections of iron demand and estimates of capital and labor requirements. Trends in technologic change and the organization of production were analyzed. Labor requirement schedules for iron ore mining and beneficiating were constructed from aggregate inter-temporal trends and 1970 cross-sectional analysis of mines and mills. A sup-ply schedule of the capital requirement for mine-mill-pellet plants was developed from U.S. and Canadian experience. The structure of demand for iron to the year 2000 was examined as well as the availability of resources. Projections of capital and labor requirements to 2000 were constructed under two international patterns of iron ore supply to the United States. The most likely model is for a continuation of the 70 percent United States-30 percent foreign shares, expanding at an average 2.0 percent growth rate to 2000, and supported by a cumulative gross capital investment of $3.8 billion constant 1967 dollars and a labor force in the United States of 29,800 by 2000. The information content of projections is discussed, and the possible effects of international forces on supply are considered. A generalized methodology for estimating capital and labor requirements in other mineral industries also is included.

Jan 1, 1975

By R. H. Sprute

Extensive Bureau of Mines laboratory testing has shown that electrokinetic densification can be an effective method for dewatering and consolidating unclassified metal mine mill tailings. The report describes results of a limited field test of this technique. Eighteen-cubic-yard concrete model stopes, 18 feet long by 6 feet deep by 56 inches wide, were filled with unclassified tailings slurry from a metal mine in the Coeur d'Alene, Idaho, district. Five different tests were performed. They showed that a strong, dense, dewatered fill can be obtained in a reasonably short time using electrokinetics, with typical power consumption of 25 to 30 kW-hr/yd3 of densified fill. At present power costs in the Coeur d 'Alene district, this would amount to 10 to 12 cents/yd3.

Jan 1, 1975

By H. E. Powell

Over 5 million lb of chromium, 1 million lb of nickel, and 90,000 lb of molybdenum are lost annually in the dusts generated in the production of stain-less steel. Additional losses of these metals in the form of mill scale and grinding swarf may be double the dust losses. This Bureau of Mines report describes a process for recovering these and other metals in the form of an alloy steel suitable for recycling. Zinc and lead, when present in the wastes, are recovered as byproducts in the form of oxide fumes. The laboratory-scale process (10-to 25-lb charges) recovers up to 95 pct of the chromium, 100 pct of the nickel, and 100 pct of the iron. The resultant alloy contains from 10 to 20 pct chromium, 6 to 12 pct nickel, and 55 to 65 pct iron, with lesser amounts of molybdenum and manganese. The alloy is essentially free of zinc, lead, and sulfur. The zinc-lead fume obtained from the treatment contains about 40 pct zinc and 20 pct lead and represents essentially complete recovery of these metals.

Jan 1, 1975

By F. N. Kissell, C. M. McCulloch, Maurice Deul, J. R. Levine

The methane content of virgin bituminous coalbed can now be measured accurately in the field with exploration core samples from vertical boreholes. The gas content of the coal per unit weight can be used either to design a mine ventilation system or to determine if degasification of the coalbed will be necessary before mining, and to determine the gas resources in the coalbed. The equipment necessary to conduct the test costs less than $50. The gas content of the coal in place in the ground is determined by summing the gas lost from coring, gas measured during desorption, and the residual gas in the coal. Upon removal from the borehole, the core sample is placed in an airtight container and desorbed for several weeks until the desorption rate is below 0.05 cm3/g for 5 consecutive days. The gas lost from the core while it was being cored and the residual gas are estimated by a new graphical method. The amount of gas remaining depends upon whether the coal is friable or blocky. Friability appears to relate to the depth of the sample below the surface, fixed carbon percentage, Hardgrove grindability index, and proximity to tectonic disturbance. Friable coals emit nearly 96 pct of the total gas during desorption whereas a blocky coal emits only 60 pct of its total gas. Coalbeds that are ill defined as to their blocky or friable nature must be tested in the laboratory for unambiguous analysis.

Jan 1, 1975

By C. M. McCulloch

The methane content of virgin bituminous coalbed can now be measured accurately in the field with exploration core samples from vertical boreholes. The gas content of the coal per unit weight can be used either to design a mine ventilation system or to determine if degasification of the coalbed will be necessary before mining, and to determine the gas resources in the coalbed. The equipment necessary to conduct the test costs less than $50. The gas con-tent of the coal in place in the ground is determined by summing the gas lost from coring, gas measured during desorption, and the residual gas in the coal. Upon removal from the borehole, the core sample is placed in an airtight container and des orbed for several weeks until the desorption rate is below 0.05 cm3/g for 5 consecutive days. The gas lost from the core while it was being cored and the residual gas are estimated by a new graphical method. The amount of gas remaining depends upon whether the coal is friable or blocky. Friability appears to relate to the depth of the sample below the surface, fixed carbon percentage, Hardgrove grindability index, and proximity to tectonic disturbance. Friable coals emit nearly 96 pct of the total gas during desorption whereas a blocky coal emits only 60 pct of its total gas. Coalbeds that are ill defined as to their blocky or friable nature must be tested in the laboratory for unambiguous analysis.

Jan 1, 1975

By J. M. Stuve

Low-temperature heat capacities and the enthalpy of formation were deter-mined calorimetrically by the Bureau of Mines for CuO?CuS04. The derived standard entropy (S°298.15) was 40.36±0.04 cal/deg-mole, and the enthalpy of formation (?H°f) was -219.l±0.3 kcal/g-mole. A large thermal anomaly was observed in the heat capacity of CuO?CuS04 at 20±0.1 K. Gibbs energy of formation data are tabulated up to 1,200 K. Construction details of a precision low-temperature adiabatic calorimeter capable of determining heat capacities of solids in the temperature range 5 to 320 K are given. A calibrated miniature germanium resistance thermometer was incorporated into the calorimeter to extend the range of accurate measurements below 15 K. High-resistance dc heater windings were used throughout the cryostat to reduce heat conduction of inner connecting wires.

Jan 1, 1975