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By Seth C. Scharfer

"As part of the Bureau of Mines effort to provide thermodynamic data for the advancement of mineral technology, the Gibbs energies of formation of MoS2 (molybdenite) and WS2 (tungsten disulfide) were determined with high-temperature galvanic cells employing stabilized Zr02 (zirconia) as the electro¬lyte. In the temperature range from 867 to 1,209 K, potential measurements were obtained for the cellPt, MoS2 , Mo02 , SO2 = 1 atm // Zr02 // 02 = 0.0112 atm, Pt, with the overall cell reactionMoS2(c) + 3 02(g, 0.0112 atm) = Mo02 (c) + 2 S02(g). (1)These results, combined with the best available values for Gibbs energies of formation (?G°f) of Mo02 (molybdenum dioxide) and SO2 (sulfur dioxide) from the literature, give the standard Gibbs energy of formation of MoS2, ?G°f, for the reactionMo(c) + S2(g) = MoS2(c) (2)?G°f = -96.681 + 43.76 x 10-3T±0.538 kcal/mole, (3)where temperature (T) is expressed in Kelvins.Similar measurements in the temperature range from 872 to 1,210 K were obtained for the cellPt, WS2 , W03 , SO2 = 1 atm // Zr02 // 02 = 0.0114 atm, Pt, with the overall cell reactionWS2(c) + 3.5 02(g, 0.0114 atm) = W03 (c)+ 2 S02(g). (4) Combination of these results with the best available data of ?G°f for W03 (tungsten trioxide) and SO2 from the literature gives the Gibbs energy of formation of WS2 in the temperature range from 872 to 1,210 K for the reactionW(c) + S2(g) = WS2 (c)(5)?G°f = -92.429 + 43.88 x 10-3T ± 0.280 kcal/mole. (6)A third-law analysis yields a standard enthalpy (?H°f) for the reaction298Mo(c) + 2 S(rh) = MoS2(c), (7)?H°f = -67.36±0.60 kcal/mole, (8)298where the standard states are pure crystalline MoS2 / and rhombic sulfur."

Jan 1, 1980

By D. E. Shanks

The Bureau of Mines surveyed a variety of inorganic ion-exchange materials to determine their suitability for removing valuable accessory elements and troublesome contaminants from metallurgical process and waste streams. Most of the materials, which included molecular sieves, heteropolyacid salts, and hydrous metal oxides, did not give adequate separations, did not have the necessary stability in strong acids or bases, or were not in a physical form suitable for ion-exchange use. Many of the suitable inorganic materials, especially the hydrous oxides, were capable of cation exchange with high capacity only in basic conditions, which caused hydrolysis of most of the cations tested. Multivalent anions, such as arsenate and phosphate, were easily removed from acidic solutions by hydrous oxides. Hydrous zirconia was the best material for this purpose. Multivalent anions were not easily des orbed because of compound formation; therefore, conventional ion-exchange techniques could not be employed. As an alternative approach, hydrous ferric hydroxide was used as a filter material to remove arsenate and phosphate from acid solutions. One gram of arsenic was removed from solution for each 20 g of ferric hydroxide. Ferric hydroxide is preferable to hydrous zirconia for use as a filter material because of low cost.

Jan 1, 1983

By P. E. Churchward

Rhenium sources and recovery methods were investigated by the Bureau of Mines to delineate potential resources of the metal. The only significant rhenium resource appears to be about 28,000 lb of rhenium contained in the domestic annual output of approximately 20,000 tons of byproduct molybdenite concentrates from porphyry copper operations. An estimated 70 to 80 pct of this rhenium is potentially recoverable by processing the rhenium-bearing fumes and dusts obtained during conventional roasting of molybdenite concentrate. At 70 pct recovery this would amount to 19,600 lb of rhenium. A more conservative estimate by the Committee on Refractory Metals of the National Research Council (1513 is that 12,000 lb of rhenium metal could be produced annually from current production of molybdenite from porphyry copper operations in the United States. A procedure was developed in the laboratory for recovering rhenium in the form of electrolytic flake by electrowinning the metal from a solvent extraction strip solution. The procedure included (1) water leaching of molybdenite roaster flue dust, (2) selective extraction of rhenium from the leach liquor by contacting it with a kerosine solution of a quaternary amine, (3) stripping of rhenium from the loaded organic solution by a perchloric acid solution, and (4) electrodeposition of rhenium from the loaded strip liquor. Raw material for the studies was flue dust containing 0.48 pct Re, 35 pct Mo, and 23 pct S in sulfide and sulfate form, and small amounts of numerous metallic impurities. Water leaching dissolved 85 pct of the Re and yielded a solution that was 13 in sulfuric acid and contained, 1 g/l Re and 16 g/l Mo. The solvent extraction strip solution that was electrolyzed for rhenium deposition was 1 molar in perchloric acid and 1 molar in ammonium sulfate and contained 13 g/l Re and 0.01 g/l Mo.

Jan 1, 1963

By E. K. Kleespies

The rate of the heterogeneous reaction between titanium-oxygen solid solutions and titanium trichloride in molten sodium chloride was determined at high temperatures. In the alpha phase, the reaction rate decreases uniformly with the increasing concentration of oxygen. The gamma crystalline form of titanium (above 33 atomic percent oxygen) was much less reactive than the alpha phase, and the reaction rate approached zero at 50 atomic percent oxygen. The activation energy for the reaction of titanium-oxygen solution containing 22.8 percent oxygen was 11.7 kcal/mole of TiCl3 as compared with 8.3 kcal/mole of TiCl3 for pure titanium.

Jan 1, 1967

By J. M. Stuve

Standard heats of formation (AH°p) of YbCl3 (c) and TmCl3 (c) were measured by solution calorimetry. Heat of solution data are given for ytterbium and thulium metals and corresponding anhydrous trichlorides in 4.360 molal hydrochloric acid. The derived standard heats of formation of YbCl3 (c) and TmCl3 (c) were -229,370 ±720 and -235,820 ±400 cal/mole, respectively, at 298.15° K. The resulting heats of formation for YbC13 and TmCl3 are about 1 kcal and 6.3 kcal more negative than previously published values.

Jan 1, 1967

By John M. Devine

Hydrogen sulphide associated with natural gas was noted as early as at Point Albino, Canada. The presence of this impurity was recognized also in other of the earlier oil and gas fields, although the occurrence was by no means common. However, in recent years, with the development of the producing zones of test Texas and the Texas Panhandle, the Production of "sour" crude has increased greatly and hydrogen sulphide has proved a generally troublesome factor--frequently a major problem--in the drilling and operation of many wells in those areas. The problems arising from the drilling and producing of oil or gas wells in hydrogen-sulphide areas, fall under two general divisions: safety problems and corrosion problems. Mention is made of a third division which is closely related to the other two, that of treating--or the development of processes for the removal of hydrogen iron the standpoint of safety and health hazards, hydrogen sulphide in the petroleum industry has been discussed in a number of publications. Likewise, the problem of hydrogen-sulphide corrosion of production equipment has been given considerable attention in the literature.

Jan 1, 1931

By William E. Bruce

The Bureau of Mines performed drill calibration tests on two industrial percussive drills of 2-5/8- and 3-1/2-inch piston diameters to determine operating characteristics for their use in conjunction with penetration rate data in developing drillability equations and furthering the knowledge of percussive drills. The use of a linear velocity transducer for measuring piston velocities and application of its instrumentation are described. Data presented include relationships between maximum piston velocity and feed air pressure other results confirm the theory or data of previous investigators, and some comparisons are made with the performance prediction formulas of other investigators.

Jan 1, 1969

By W. N. Marchant

The Bureau of Mines performed chemical research to elaborate details of sulfur chemistry pertaining to the citrate flue gas desulfurization process in which sulfur dioxide (SO2), absorbed (as bisulfite ion) in a buffered sodium citrate solution, is reduced by hydrogen sulfide (H2S) according to the overall reaction 2H2S + HSO3 + H+ ? 3S + 3H20. The rate-limiting step in the process was shown to be the reduction by H2S of thiosulfate (S2031-) that is formed as an intermediate. Pseudo first-order kinetic measurements were made at room temperature to retard the reaction sufficiently that adequate analysis was possible. These measurements showed the rates of the following net processes to be -d [S02]/dt (pH 4.5) = (0.409±0.050)min-1 [S02]; d [S2032-]/dt (pH 4.5) = (0.199±0.017)min-1 [S02]; -d [S2032-]/dt (pH 4.0) = (0.0437±0.0265)min-1 [S2032-]~1; -dH2S/dt (pH 3.9) = (21.6±3.0) mmoles/min-atm [H2S]g1.4, where [H2S]g is the partial pressure of H2S in the gas phase, in atmospheres, and the rate describes the consumption of H2S, in millimoles per minute; d[S]/dt (pH 4.0) = (38.0±3.4)min-1 [H2S]1, where [H2S] is the concentration of H2S in solution. Hydrogen ion consumption during the slow phase of regeneration was shown to occur at (2.1±0.5) times he rate of thiosulfate consumption, which is interpreted as evidence for the following as the rate-limiting reaction: 2H2S + S2032- + 2H+ ? 4S + 3H20 A scheme consisting of five sequential general reactions is proposed to account for sulfur formation.

Jan 1, 1981

By R. L. Brown, H. G. Berger, E. F. Pohlman

"The Bureau of Mines in cooperation with the American Gas Association investigating the relation of properties of gas oils to the gum-forming properties of carbureted water gas. The present report deals with the effects of operating practice on the composition of the light oils from carbureted water gas. A general outline of the gummy meter problem has been presented in a previous paper.*Carbureted water gas is a mixture roughly of 80 per cent water gas by volume and 20 per cent oil gas. The latter, though small in relative volume, supplies more than half of the heating value of the gas under the present-day standard. Therefore, it is logical that the oil used in the carbureting process and the operating practices involved should be subjected to scientific study. Many investigations***** bearing on the aspects considered in this paper have been carried out in the past."

Oct 1, 1923

By C. H. Riggs

This report describes the geology and reviews the oil-production history of the Dutcher sands of Pennsylvania age in the Muskogee oilfield. The geology and production history are presented not alone as a review of the past behavior of the field but also to interpret the possibilities for future production of oil from semidepleted sands in this and similar areas. The Muskogee field, one of the oldest oil-producing areas in Oklahoma, yields paraffin-base oil of 40° API gravity -a gravity higher than that of most Oklahoma oils. Oil was discovered in the townsite of Muskogee in 1894 but was not produced in commercial quantities until 1904. A peak yearly rate of 1,340,000 barrels of oil was attained in 1910 (see table 1).

Jan 1, 1959

By Margaret R. Egan

This Bureau of Mines report presents results from experimental studies on wood crib fires in an intermediate-scale fire tunnel. Gas concentrations, smoke particle characteristics, heat release rates, and ventilation rates were determined. These measurements form a data base for wood, which can be used with previous analyses for coal and future studies of other mine combustibles, to comprehend the potential hazards of these materials in underground mine fires. A knowledge of the combustion products emitted from these materials will benefit fire detection and control. Results show the changes in burning rate and heat release rate produced by different crib configurations and ventilation rates. Also included are the effects that the burning rate has on smoke characteristics and gas production.

Jan 1, 1986

By Robert T. Langland

The Bureau of Mines, at its Denver, Colo., research center, has developed a computer program to solve nonlinear regression problems. The program is written in a general form so that, regardless of the functional relationship assumed, the unknown parameters may be evaluated by the Newton-Raphson method of iteration. Variances and covariances of the parameters are derived, based on the propagation of errors. A creep function is established from shale test data as an example of program utility. Program accuracy is compared to the accuracies of other programs in present day use.

Jan 1, 1974

By M. M. Fine

This report presents the results of laboratory mineral-dressing investigations by the Bureau of Mines of 14 individual or composite character samples from deposits in the Batesville manganese district. It will be noted that some concentrates have met or approached analytical specifications for metallurgical manganese ore although great variations in both physical and chemical composition from once deposit to another make each a new problem. In most cases it is evident that a substantial loss of manganese has occurred in the various slime and tailing products. An important aspect of this work is the research being conducted on manganese-bearing limestones. Recent reconnaissance indicates that this resource constitutes one of the major domestic reserves of manganese. Laboratory study has shown that ferrograde concentrates can be recovered from samples of manganese-bearing limestones from two properties. Research on samples from other areas is still underway.

Jan 1, 1957

By David C. Byrne

PURPOSE: Evaluate practical technological advances in level-dependent hearing protectors and inexpensive personal acoustic monitors. RESEARCH SUMMARY: The results of previous NIOSH research show that miners develop hearing loss much more quickly than nonoccupationally noise-exposed individuals and that miners experience a greater severity of hearing loss than would be expected for nonoccupational noise-exposed persons of the same age and gender. Using hearing thresholds at 4,000 Hz as an indicator, coal miners experience hearing loss 2.5 to 3 times greater than would be expected for persons not exposed to occupational noise. At age 50, 90% of coal miners and 49% of metal/nonmetal miners were found to have a hearing impairment. In comparison, only 9% of a nonoccupationally exposed control group had a hearing impairment at age 50. There are numerous barriers to the prevention of hearing loss among miners. In an effort to overcome some of these obstacles, this work was initiated to evaluate practical technological advances in level-dependent hearing protectors and inexpensive personal acoustic monitors. Experiments will involve analysis of this new technology under both laboratory and field conditions. Laboratory components will consist of controlled studies using an anthropometrically correct test fixture as well as human subjects to evaluate the adequacy/effectiveness of various hearing protective devices. Electroacoustical performance testing of new noise monitors will also be conducted in a laboratory setting. Subsequent field studies will determine the actual usefulness and practicality of the personal protective/monitoring equipment as used in different mining situations. It is anticipated that increased on-the-spot awareness of hazardous noise levels and the availability of better-suited hearing protectors will provide a degree of protection beyond what is currently attained in different mining environments. Therefore, the intent of this project is to identify and adapt new acoustical technologies and products that have a direct application to individual mine workers. With increased knowledge of these technological advances, a greater demand for similar devices will likely occur, which, in turn, will lead to a better understanding and awareness of hearing loss prevention methods throughout the mining community. The ultimate goal is for widespread integration of useful hearing loss prevention products and devices into the daily routines of miners

Jan 2, 2000

By N. A. Eilertsen

Eastern Aroostook County, Maine, contains an enormous tonnage of manganese widely distributed in manganiferous sedimentary beds composed of hematitic shale, hematitic slate, and laminated siliceous carbonate rock. The bedded deposits range in thickness from several feet to over 150 feet. Manganese minerals that occur as silicates and carbonate are so minute that they cannot be concentrated by present methods of ore dressing. From a hydrometallurgical standpoint, the deposits can best be classified by amenability to acid leaching. The deposits of Aroostook County are in three geographical groups (see fig. l), designated as the northern, central, and southern districts. At least 13 deposits are known to occur in the latter district, which covers an Ewes about 8 miles wide and 15 miles long. The Littleton Ridge deposit, on the northern boundary of the southern district, previously examined by geologists from the State and Federal Geological Surveys on the farms of Donald H. Haggerty and David A. Abernethy, was pointed out in reports as being possibly the richest and largest in the southern district. The Bureau of Mines sampled this deposit by surface trenching and diamond drilling from May 1 to September 30, 1951. A total of 23 trenches was bulldozed, aggregating 5,355 linear feet, of which 8 trenches were sampled by cutting 185 channel samples over a linear distance of 1,820 feet.

Jan 1, 1955

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 D. E. Wolfson

This report presents 900° C BM-AGA carbonization and related data for coals from the principal beds of Nicholas, Randolph, and Webster Counties, W. Va. Thirty-three samples from nine coal beds in three counties were car-bonized at 900° C in the l8-inch-diameter BM-AGA retort, data from which have been correlated with industrial production. Host of the samples were chemically suitable for metallurgical use, and their coking properties were satisfactory. Except for four of the Lower Kit-tanning samples, the ranges of constituents in the coal seams were 1.8 to 9.0 percent ash and 0.4 to 1.1 percent sulfur, values within the range of accept-ability for metallurgical coals. Coke strength indexes were normal for Appalachian coals of similar rank, and the tumbler stability indexes of the coke ranged from 35 to 57.

Jan 1, 1969

By E. H. Denny

In discussing safety in Colorado metal mines there are two important points for metal -mining men to consider , namely , the direct and indirect cost of accidents and the possibility and means of preventing accidents . For statistics on Colorado metal - mine accidents , reference has been made to published reports of the United States Bureau of Mines on metal- mine accidents from 1919 to 1927. This period was considered because only with the year 1919 are complete figures on nonfatal accidents available and because these years represent postwar activities ; 1927 is the last year for which the U. S. Bureau of Mines has published accident statistics . During the nine -year period 1919 to 1927 , inclusive , 153 metal miners were killed by mine accidents in Colorado and 5,035 miners suffered lost - time injuries . The accidentfrequency rate of number killed per 1,000 300- day workers for this nine - year period was 4.68 as compared with the general average of 3.26 for all the metal mines of the United States for the same period . In other words , the fatality rate in the metal mines of Colorado for this nine- year period averaged 40 per cent higher than that of the metal- mining industry in the United States generally . In 1924 and 1926 the Colorado metal mines had a better accident record than the average of those of the United States , but 1927 was a bad accident year and the State Bureau of Mines figures for 1928 and 1929 showing respectively 18 and 23 men killed in and about the metal mines indicate a continuing relatively high death rate from accident . The cost of accidents to the miner for the period 1919 to 1927 can be estimated from the accident figures just given . The United States Bureau of Mines as well as other authorities assess 6,000 days lost time for every fatality and every permanent total disability . These authorities have also agreed that a permanent partial disability costs 800 days lost time to the worker over his working lifetime , that lost time injuries of less than 14 days average about 6 days lost time and lost time injuries not involving permanent disability but having loss of more than 14 days average 32 days lost time . On this basis the Colorado metal miners have suffered in nine years a gross loss of 1,214,146 days , or , at $5 per day , $6,070,730 . The miner receives about one -ninth of this amount in compensation so that the net loss to the metal miner in Colorado for this nine - year period was about $5,400,000 .

May 1, 1930

By R. Blickensderfer

Several thin film absorber stacks with spectrally selective characteristics were developed by the Bureau of Mines. The stacks consisted of a silicon thick film or a zirconium compound thin film on a reflective thin film of silver. The zirconium absorber films, with the general formula ZrCxOyNz, were prepared by reactively sputtering zirconium or zirconium carbide in argon with small amounts of oxygen, nitrogen, or both, or by oxidizing zirconium films in air. A few similar types of films were prepared from titanium. The short-wave absorptance over the solar spectrum, a(s), and thermal emittance at 600 K, e(600 K), of the solar absorber stacks were calculated from room-temperature reflectance data. The values of a(s) ranged from 0.47 to 0.93, e(600 K) from 0.49 to 0.034, and the ratio a(s)/e(600 K) from 1.7 to 34. The specimen with the best combination of properties, a ZrNx-Ag stack, had a solar absorptance a(s) of 0.85 and a ratio, a(s)/e(600 K), of 24. The effect of film thickness and composition on spectral selectivity was determined. An emissometer for measuring normal total emittance up to 800 K and a method for determining a (s), e(T) (hemispherical), and a(s)/e(T) using simulated solar radiation are described. A calorimetric method for measuring a(s) and e(T) (hemispherical) at elevated temperature is also described. Measurements made on several specimens agreed favorably with calculated values.

Jan 1, 1976

By Henry E. Blake

The Bureau of Mines has been engaged in a continuing research effort to develop processes for increasing the recovery and utilization of fluorine from low-grade resources. This current research has shown that over 98 percent of the fluorine in phosphate rock is extracted when the ore is treated with excess phosphoric acid in the presence of water vapor at 150° to 180° C. More than 80 percent of the fluorine can be recovered as fluosilicic acid, which can then be converted to commercially useful hydrogen fluoride or fluorspar by previously developed Bureau processes. Extraction of P205 from the ore was about 98 percent in batch tests and 90 percent in semicyclic tests.

Jan 1, 1974