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By F. S. Karn

Measurements were made of the flow of helium, methane, ethane, butane, and toluene through thin disks of coal. All measurements were made on a dense layer in the Pittsburgh seam identified as attritus. Flow increased with pressure differential and temperature. At room temperature and a pressure differential of 1 atmosphere flow rates along the bedding plane of Pittsburgh seam coal were helium 881 X 10-10 cm2 sec-1, methane 1.2 X 10 -10 cm2 sec-1, ethane 0.54 X 10-10 cm 2 sec-1, n-butane 0.35 X 10-10 cm2sec-1, and toluene 3.8 X 10-10 cm2sec-1. Flow rates were 50 percent lower across the bedding plane of the coal than along the bedding plane. Activation energies were 3.9 kcal mole-1 for helium and 13.6 kcal mole-1 for methane, with diffusion measured either along or across the bedding plane.

Jan 1, 1970

By W. H. Oppelt

A small, annular-retort gasifier having a nominal capacity of 40 pounds of lignite per hour was designed and constructed at the Lignite Experiment Station, Grand Forks, N. Dak. The purpose of the investigation was to increase the capacity of an annular-retort gasifier by better temperature distribution in the heating chamber (adjacent to the annulus) and by supplemental internal heating with controlled amounts of air. Correct control of air admission should yield crude ammonia-synthesis gas having a (H2+CO)-N2 ratio of 3. Dakota Star stoker-size lignite was used during the exploratory experimental program. The effects of temperature level and distribution in the heating chamber and of addition of air to the reactor were investigated. Hydrogen - carbon monoxide ratios ranged from 1.9 to 2.5, and (H2+C0)-N2 ratios were as low as 2.9. Hourly gas production ranged from 970 to 2,580 cu. ft., or 62.0 to 164 cu. ft. per sq. ft. of heated surface, or 350 to 940 cu. ft. per cu. ft. of reactor volume. Data from the small gasifier could be readily correlated with those previously obtained in the commercial-scale unit under comparable experimental conditions.

Jan 1, 1957

By Irven A. Jacobson

The thermal reactions of l-methylindole were studied in the temperature range of 525° to 627° C in a flow reactor. The major products consisted of 2-methylindole, 3-methylindole, indole, quinoline, hydrogen, and methane. 2-Methylindole is formed from 1-methylindole by an irreversible isomerization reaction. The 2-methylindole isomerizes in a reversible manner to 3-methyl-indole, the equilibrium favoring the 3-methyl isomer. Indole is formed directly from 1-methylindole. Quinoline is formed from l-methylindole, 2-methylindole, and 3-methylindole.

Jan 1, 1971

By Agnes Y. Lee

As part of the U.S. Bureau of Mines program to improve base metal leach systems, pressure leaching of galena (PbS) concentrates in fluosilicic acid (H2SiF6) solution was investigated. Lead extraction was 93 pct when PbS was pressure leached in H2SiF6 at 95° C with 2OO-psig O2 pressure for 40 min, using ferric nitrate [Fe(N03)3] as a catalyst. The effects of several catalysts, O2 pressure, time, and acid concentration on leaching were determined. The purified leach solution was electrowon to recover high-purity Pb metal. The H2SiF6 used in leaching and electrowinning can be recycled continuously. A flow diagram was proposed based on this investigation. Elemental sulfur (SO) was recovered from the leach residue by solvent extraction. A method was also developed for treating the flnal residue to segregate the important byproduct elements such as Ag, Cu, and Zn and enable their recovery by standard commercial processes.

Jan 1, 1990

By R. K. Koch

The vapor pressures of liquid molybdenum and liquid zirconium were determined by the Langmuir free-evaporation method. An electron-beam furnace with a water-cooled copper crucible was used for melting. Temperature was measured with a two-color ratio pyrometer. The vapor-pressure data led to the following equations: [log p (atm) = 5.429 - 28,380 T for liquid molybdenum in the range 2,890° to 2,990° K, and log p (atm) = 6.521 - 30,940 T for liquid zirconium in the range 2,229° to 2,795° K.] Third-law evaluations of each data set gave mean heats of sublimation (298.15° K) of 157.6 ± 1.8 kcal/mole and 148.4 ± 2.4 kcal/mole for molybdenum and zirconium, respectively, where the uncertainties are two standard devia¬tions. Second-law standard heats of sublimation determined from sigma plots and tabulated enthalpies were 143.5 ± 2.7 kcal/mole and 149.2 ± 3.8 kcal/mole for molybdenum and zirconium, respectively. The better agreement in heats of sublimation for zirconium is attributed to the 566° K temperature range studied which permitted a more accurate definition of the vapor pressure curve than could be obtained from the 100° K span for molybdenum. This supposition was verified by making a sigma-prime plot which utilized solid vapor pressure data for molybdenum to extend the evaluation range by 800° K. This gave a standard heat of sublimation of 155.2 ± 1.6 kcal/mole which is in good agree¬ment with the third-law value. The plot also gave a standard entropy of sublimation (298.15° K) of 35.73 ± 0.48 eu.

Jan 1, 1968

By Joan C. Biordi

[Composition profiles for atomic, radical, and stable species, as well as temperature and area expansion ratio profiles, have been determined for a nearly stoichiometric CH4-02-Ar flame and one to which 0.3 percent CF5Br inhibitor had been added. Net reaction rate profiles were calculated for all the observed species. For the normal flame, these and the mole fraction profiles gave rate coefficient information about the elementary reactions in the methane flame, for example, CH. + 0 4- H2CO 0 H, k4 = 1.05 X 1014CM3 mole-1sec-1 for 1,550§T 0,725' K; CO + OH 4 C02 + H, k6= 4.7 X 1011 for 1,350{T X1,750° K. Comparison between the inhibited and normal flame showed that A] and [CH3] were significantly reduced at the lower temperatures in the inhibited flame even though in the hot gas region the [E] [OH!, and [0] were essentially the same in both flames. The CF3Br disappears very early in the flame, relative to the fuel, and the reaction primarily responsible for its disappearance is H v CF3Br 4 HBr + CF3, where k7 is found to be 2.2 X 1014 exp(-9460/RT) for 700-1,550° K. Reaction of the inhibitor with methyl radicals provides for the relatively small amounts of CH3Br observed, but CH3 + Br2 - CHs Br + Br must also occur. The HBr formed reacts rapidly with H atoms to form H2 and Br, but the reaction is soon "balanced" in the flame as may be demonstrated by calculation of the equilibrium constant at various temperatures. The fluoro-carbon fragment produced in reaction (7) also reacts rapidly, in part with methyl radicals to give the observed elimination product CH2CF2 Later in the flame, above -1,400' K, F2CO is formed from the reaction CH2CF2 + 0 P F2CO + CH2 and k., -1.5 X 1013 at 1,600° K. The rather slow decay of carbonyl fluoride is attributed to reaction with H atoms according to the sequence F2CO I H - HF + FCO and FCO + H HF + CO.]

Jan 1, 1975

By R. R. Falier, W. E. Rice

"PURPOSE OF REPORTThis paper presents the results of a series of tests made by the U. S. Bureau of Mines in cooperation with The Ohio State University Engineering Experiment Station as part of an investigation on the use of fuel in kilns.This report is preliminary and gives only enough of the test data to illustrate results and show the reasons for the successes and failures of the method of firing investigated; fuller details will be included in the final report.PERSONNEL FOR TESTSThe investigation is conducted under supervision of P. Nicholls, supervising fuel engineer, of the United States Bureau of Mines, and G. A. Bole, research professor, of The Ohio State University. These tests were made under direction of W. E. Rice, associate fuel engineer, assisted by R. R. Faller, assistant fuel engineer, of the United States Bureau of Mines; H. C. Harrison, senior research engineer (until October 1, 1930), C. R. Austin, senior research engineer (since October 1, 1930), and H. K. Van Sohoick, junior research engineer, of The Ohio State University. M. J. Rice, field engineer, represented the manufacturer of the stoker.PURPOSE OF INVESTIGATIONThe general aim of the investigation is to develop more economical methods of using fuel in kilns and to improve the over—all efficiency of the process of firing by methods that will produce ware of better quality. One phase of this investigation is the burning of coal on an automatic stoker to gain the advantages of control, constant rate of application of heat, and ability to burn cheaper coal than can be used in the hand—fired furnaces of kilns. It a stoker in to be used it is desirable that the coot of the installation should be low, the control of operation simple, and the distribution of heat in the kiln as good or better than with hand firing. These desiderata were sought in the stoker and furnaces that were used for the tests described herein. The tests were made to determine whether it is feasible to fire a large kiln with a single stoker, whether the use of a single furnace simplifies control, and whether the admission of all the hot gam at the center of the kiln will give symmetrical distribution of heat."

Aug 1, 1931

By Fred C. Turin, Jasinder S. Jaspal, Alan G. Mayton, William J. Wiehagen

This report describes serious injuries occurring to bulldozer operators working at U.S. coal, metal, and nonmetal mines. The period covered is 1988-97. The data were collected by the Mine Safety and Health Administration (MSHA). A total of 873 injury records are examined. These injuries resulted in 18 fatalities and 31,866 lost workdays. All of these injuries occurred to dozer operators while they were doing common production tasks. An injury classification system was developed to code the narrative information that describes the circumstances surrounding the injuries. Injury records are categorized by activity (task being done), incident result (what apparently happened to the dozer), and operator impact (how the operator was injured). Where information is available, contributing factors are identified. This classification system supplemented the standard injury/illness data classification system compiled by MSHA. The results of the study indicate that, from 1993 to 1997, the number of serious injuries to dozer operators declined by 30%. The reduction in serious injuries was accompanied by a decrease in days lost due to injury. Although the number of reported injuries has decreased, dozer operators being jolted and jarred accounts for the largest percentage (70% of the incidents) and severity (75% of the workdays lost) of serious injuries while operating the equipment. Vertical jars (while backing up the dozer) resulting in injury to the operator accounted for a sizable percentage of jolting and jarring injuries. Working near an edge carries significant risk for fatal injuries. Of 116 incidents where the dozer fell over an edge, rolled over, or fell into a hidden void, 14 (12%) resulted in fatal injuries. In cases where the dozer operator either jumped or was thrown out of the cab in a fall over or rollover, 7 out of 26 were killed. Overall, 80% of the fatalities occurred while working near an edge or hidden void or on a steep slope. Further reductions in injury risk will require more widespread use of seatbelts, field and laboratory research interventions to better assess the effect of alternative engineering (e.g., seat and seat suspension) designs to dampen or isolate the effects of shock and vibration, and continued focus on hazard awareness, recognition, and response.

Jan 4, 2001

By R. B. Anderson

As a part of a Bureau of Mines program on the conversion of coal to liquid and gaseous fuels, the kinetics of the Fischer-Tropsch synthesis on iron catalysts was investigated. Nitrided catalysts were studied at 21.4 atmospheres using feed gases ranging from 2H2+1CO to 0.25H2+1CO, and at 7.8 to 21.4 atmospheres using 1H2+1CO gas. The overall apparent activation energy increased with increasing carbon monoxide content of the feed gas from 19.5 kcal/mole for 2H2+1CO to 23.7 for 0.7H2+1CO. The rate of synthesis with 1H2+1CO feed increased linearly with operating pressure from 7.8 to 21.4 atmospheres. A semifundamental rate equation of the form [r=a'PH2 0.6pco 0.4- ?r0.5PH200.5] was shown to fit the data satisfactorily. The relative usage of hydrogen to carbon monoxide decreased with increasing conversion, passed a minimum, and then increased. Apparently water is the principal primary product and carbon dioxide is produced by subsequent water-gas shift reaction. In another group of experiments water, carbon dioxide, argon, and methane were added to 1H2+1CO feed to a nitrided iron catalyst. Argon and methane were only diluents. Carbon dioxide was a slight inhibitor and water vapor was a strong inhibitor to the rate of synthesis. Water accelerated the water-gas shift and usually increased methane production. Important factors of catalyst geometry in determining rate were found to be particle size and extent of reduction. Apparently the active portion of the catalyst is confined to a layer of 0.01 to 0.02 cm from the external surface of particles. A special solution was made of differential equations relating re¬action at the catalyst surface to diffusion in pores of the catalyst for spherical particles with an active layer surrounding an inert core. The equation derived expressed the experimental data reasonably well. Diffusivities determined by this equation varied from 3 to 24X10-6 cm2/sec; these values are of the same magnitude as observed for the diffusion of gases in liquid. The appendix presents a group of synthesis experiments at pressures of 21.4 to 103 atmospheres. In this range the rate of synthesis on nitrided iron catalysts increased with pressure to the 0.74 to 0.84 power.

Jan 1, 1964

By H. L. Retcofsky

Carbon-13 nuclear magnetic resonance (18CNMR) spectra of nine 2-substituted pyridines, seven 3 -substituted pyridines, and nine 4-substituted pyridines have been obtained and analyzed. Substituents included both electron-releasing groups and electron-with hawing groups. Substituent effects on the magnetic shieldings of the ring carbons, except for those in the 2-positions of 2-substituted pyridines, were found to be quite similar to the effects reported for the monosubstituted benzenes, Thus, at least to a first approximation, the two classes of compounds have similar shielding mechanisms. Shieldings of the carbon atoms in the 5-positions of 2-substituted pyridines and those in the 6-positions of 3-substituted pyridines were found to reflect electron release or withdrawal by substituent groups, The pyridinium cation and the compounds 2,2'-dipyridyl and benzonitrile were also investigated.

Jan 1, 1969

By Harold H. Fukubayashi

The effect of various zinc electrowinning solution impurities on the surface morphology of deposited zinc was investigated. Impurities studied included Al, Ag, Cd, Co, Cr, Cu, Ge, Mn, Ni, Sb, Sn, Ti, Pb02, PbSO4, and HC1. Also, the effect of animal glue, gum arabic, and Na2SiO3 additives on the deposited zinc surface structure was studied. Results were compared with deposits from a pure electrolyte consisting of H2SO4 and Zn+2, 200 and 65 gpl, respectively. Zinc was deposited on a Al cathode, 99.9 pct pure, using Pt anodes. Time, temperature, current density, and impurity concentrations were con¬troller The bulk of the tests were conducted at 40° C and 75 A/ft2 (82 mA/cm2). A scanning electron microscope (SEM) was used to examine the surface morphology. X ray diffraction techniques were used to determine crystal orientation and nondispersive X-ray spectrometer analyses were employed in an attempt to locate impurity concentrations on the zinc deposit when pitting or re-solution occurred. The impurities were categorized by their effect on current efficiency, morphology, and apparent mechanism of H2 evolution from the cathode.

Jan 1, 1974

By L. C. George

The Bureau of Mines measured the vapor pressures of selected mixtures in the binary systems CdCl2 ?SnCl2, CdCl2 -ZnC12, PbCl2 ?SnCl2, and PbCl2 -ZnCl2 by the static pressure method. These data were evaluated by the second-law (sigma-plot) method. Equations expressing the vapor pressures and the heats and free energies of vaporization as functions of temperature are given.

Jan 1, 1969

By Kihong Park

A hygroscopicity tandem differential mobility analyzer (HTDMA) technique is used to determine size-effect of nanoparticles (NaCl, (NH4)2 SO4, KCl, NH4NO3, MgCl2,CaCl2) on their hygro­scopic properties (deliquescence relative humidity (DRH) and hygroscopic growth factor (GF)). The HTDMA system uses a combination of two nano DMAs and two regular DMAs to measure particle size change in a wide dynamic particle size range. Particles are subsequently analyzed with a transmission electron microscopy to investigate the potential effect of particle structure or morphology on the hygroscopic properties. We found that structural properties of NaCl and (NH4)2SO4 particles also play an important role in determination of the DRH and GF and are more pronounced at smaller diameters. Data show that the DRH of NaCl nanoparticles increased from *75% up to *83% RH at 8 nm and that their GF decreased with decreasing size. The extent to which the GF of NaCl nanoparticles decreased with decreasing size was greater than theoretically predicted with the Kelvin correction. The GF of furnace-generated NaCl nano­particles that have pores and aggregate shape was found to be smaller than that of atomizer-generated particles that are close to perfectly cubic. For the case of atomizer-generated (NH4)2SO4 nanoparticles, we observed no signi?cant size-effect on their DRH, and the measured GF agreed well with predicted values using the Kelvin correction. For furnace-generated (NH4)2SO4 nanoparticles, a gradual growth at moder­ate RH without noticeable deliquescence behavior occurred. Their TEM images showed that contrary to atomizer-generated (NH4)2SO4 nanoparticles the fur­nace-generated (NH4)2SO4 nanoparticles are not perfectly spherical and are often aggregates having pores and holes, which may favor holding residual water even in the dried condition. For atomizer-generated KCl, MgCl2, and CaCl2 nanoparticles, we observed no signi?cant size-effects on their DRH and GF for the mobility size as small as 20 nm.

Jan 1, 2008

By H. C. Ko

Calorimetric determinations of low-temperature heat capacities and standard enthalpy of formation were made by the Federal Bureau of Mines for basic aluminum sulfite, A1203?2.0S02?5.3H20. The standard values of entropy (S°), enthalpy of formation (?Hf°), and calculated Gibbs energy of formation (?Gf°) at 298.15 K are 85.2±0.1 cal/deg-mole, -943.1±1.2 kcal/mole, and -820.7±1.2 kcal/mole, respectively.

Jan 1, 1976

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 Larry A. Haas

The chemistry of current or potential SO2 removal processes can be placed into four categories: (1) reduction, (2) Liquefaction, (3) direct dissolution, and (4) oxidation. Methods that involve reducing SO2 to elemental sulfur appear promising since this product can be easily handled, shipped, and stock- piled. Unfortunately, SO2 cannot always be reduced directly when other oxidizing agents are present. Thermodynamic data indicate that some oxidizing reagents will also consume reductant at the reduction temperature. A two- stage process can be applied to waste gases that contain excessive quantities of oxygen, nitrogen oxides, and water vapor. The best sorbent for the first stage appears to be a nonalkali or nonalkaline earth medium since this medium more readily releases the SO2 for reduction in the second stage.

Jan 1, 1973

By J. J. Lukasko

The U.S. Bureau of Mines developed an alternative electrochemical process for the production of calcium metal. The current industrial practice is costly, complex, and inefficient. The Bureau method involved electrowinning of a calcium-tin alloy followed by electrorefining to produce calcium metal. In the electrowinning cell, CaCI2 was fed to a KCI2-CaCI2 electrolyte. The calcium was electrowon at 6500 C into the pure molten tin cathode until the cathode contained 7.5 wt pct Ca. Current efficiency for electrowinning averaged over 90 pct. The resulting calcium-tin alloy served as the anode for the electrorefming cell, which employed a [CaC~-CaF2] fused salt as the electrolyte. Calcium metal was electrorefmed at 8500 C with a current efficiency of 85 pct based on calcium metal recovered. The calcium metal analyzed 99.2 pct, which is purer than commercially produced calcium.

Jan 1, 1990

By Charles W. Huggins

The Bureau of Mines investigated palygorskite, a natural asbestiform material, to accumulate knowledge that might serve as a foundation for future synthesis of a similar material. Unit cell, chemical analysis, DTA, TGA, optical constants, and electron microscopy data were obtained. Selected palygorskite samples of bettor than 97-percent purity were used to obtain this information. Chemical analysis revealed the following formula: (OH2)4 (OH)2 Ca0.01Fe0.02K0 .c3Mg2.10A12.00Si7.93020.3.91 H2O. The optical constants for sodium light are a = 1.522; S = 1.530; ?=1.533; biaxially (-). The following orthorhomibic unit cell constants were determined: ao = 12.690 A, Z = 2, bo = 17.857 A, Dx = 2.327. co = 5.207 A, Identical diffraction patterns resulted from the three palygorskite samples that were studied. X-ray, chemical, DTA, TGA, and optical data were compared with literature values for similar fibrous materials. X-ray diffraction lines were indexed. Several electron micrographs were made to compare the structures of palygorskite and attapulgite with that of chrysotile. The micrographs revealed extremely short laths for attapulgite, very long flexible laths for palygorskite, and tubular structure for chrysotile.

Jan 1, 1962

By P. C. Good

The Bureau of Mines conducted a laboratory investigation of a sinter-leach method to recover aluminum and fluorine from waste carbon potlining residues from secondary cryolite recovery operations in aluminum reduction plants. After removal of carbon by burning, the residue was sintered at 900° to 1,100° C with silica and N2CO3, then crushed and leached with dilute NaOH solution, dilute Na2C03 solution, water, or water containing residual Na2O which remained in the sinter after reaction and decomposition of Na2CO3. Over 90 percent of the contained aluminum and up to 87 percent of the contained fluorine were extracted from this waste product in the form of a mixed alkaline solution. Treatment of the alkaline solution with CO2 yielded a white precipitate containing 89 percent of the original aluminum and 61 percent of the original fluorine as a mixture of synthetic cryolite and alumina, together with a variable excess of soda.

Jan 1, 1969

By R. K. Koch

The vapor pressures of liquid titanium and liquid platinum were studied under the Bureau of Mines program for the determination of thermochemical data on the transition elements. Beating was done in a 2-kw electron-beam furnace with a water-cooled copper crucible to contain the melt. Temperature was measured with a disappearing-filament brightness pyrometer. The vapor pressure data for liquid titanium in the range 2,008° to 2,379° K are represented by the least-squares derived equation [log p (atm) = 6.268 - 22, T] Two series of determinations were made on liquid platinum. Results of the first series are expressed by the least-squares derived equation [log p (atm) = 8.240 - 30,460T] for the range 2,0860 to 2,4200 K. Results of the second series are expressed by the least-squares derived equation [log p (atm) = 7.795 - 29,580 T] in the range 2,045° to 2,442° K. Third-law evaluations of each series gave mean standard heats of sublimation of 112.4 kcal/mole, 133.3 kcal/mole, and 133.8 kcal/mole for titanium first series on platinum, and second series on platinum, respectively. Second-law heats of sublimation and equations for heats, free energies, and entropies of vaporization were obtained from sigma plots of each data set.

Jan 1, 1969