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By D. C. Fleck

The Bureau of Mines, in a cooperative research program with four lead companies, has investigated ferric chloride leaching of galena to prepare lead chloride for molten-salt electrowinning to produce lead metal. The hydrometallurgical-electrolytic process is an alternative to the sintering-smelting-refining process currently used to produce lead metal and avoids the environmental problems associated with a conventional smelter. During investigations on the electrowinning aspects of the work, it was noted that certain cations, moisture, and sulfate in the electrolyte affect lead metal purity, cell voltage, current efficiency, and viscosity of the electrolyte. Results of bench-scale tests are re-ported on the effects of CaCI2, CuCI2, FeCI2, MgCI2, NaCI, ZnCI2, PbS04, and moisture on electrolysis. As impurities increased in the electrolyte, current efficiency decreased. CaCI2, CuCI2, and FeC12 decreased current efficiency by 12 to 47 pct. ZnCl2 gave a small voltage increase, while CaCI2 addition equivalent to 4.9 pct Ca caused a 50-pet increase in voltage. The lead metal was contaminated in direct proportion to the CuCI2 buildup in the electrolyte, Anode corrosion was observed with MgCI2 and MgC12?6H20. Viscosity increased appreciably with the buildup of NaCI, CaCI2, and sulfate. Electrolyte foaming occurred with ZnC12, MgC12?6H20, MgC12, FeC12?2H20, and FeCI2. Moisture inhibited the coalescence of the lead metal.

Jan 1, 1983

By A. E. Back

[Several processes for recovering manganese from low-grade ores have been proposed3/4/5/ in which an aqueous slurry of the ore is leached with gas containing nitrogen, oxygen, and sulfur dioxide as obtained from burning sulfur or roasting sulfide ores. The manganese dioxide is dissolved, and most of the sulfur dioxide is oxidized to sulfate, but an appreciable quantity of dithionate is usually formed, together with acid from oxidation of the sulfur dioxide. The over-all reactions may be represented as follows: (1) Mn02 + S02 = Mn++ + S04--. (2) Mn02 + 2S02 = Mn++ +S206--. (3) H20 + So2 + 1/2 02 = 2H+ 5S4--. (4) H20 + 2S02 + 1/2 02 = 2H+ + S206---.]

Jan 1, 1952

By Elton L. Litchfield

The Bureau of Mines determined minimum energies for direct initiation of expanding gaseous detonation waves in acetylene-oxygen mixtures. Composition limit ranges for the initiation of detonation with fixed energies have been compared to data in the literature. Assuming that the stored electrical energy is completely converted to thermal energy, the agreement between the energy of primary explosive initiators and the energy of electrical discharge initiators was good. Minimum energies for initiation of detonation in the most sensitive composition (40 percent C20 plus 60 percent 0 2) were: 0.64 joule at an initial pressure of 1/4 atmosphere, 5.0X10-2 joule at 1/2 atmos¬phere, and 3.7X10-3 joule at I atmosphere. Fuel concentrations in mixtures initiated to detonation by 4.9X102 joules ranged from 10 to 65 percent C2H2 at 1/4 atmosphere, 10 to 67 percent C2H2 at 1/2 atmosphere, and 9 to 68 percent C2H2 at 1 atmosphere.

Jan 1, 1967

By H. R. Beard

The citrate process for sulfur dioxide emission control was developed in pursuit of the Bureau of Mines goal of minimizing the adverse environmental impact of mineral-processing operations. This publication describes the gas analysis procedures used during development of the process. The research required the capability to analyze SO2, H2S, CO, CO2, COS, volatile hydrocarbons, NO, NO2, O2, N2, and H2. The methods described include gas chromatography, electrochemical detection, infrared spectroscopy, and the use of a computer program to predict the product composition in complex reactions. Laboratory and pilot plant applications are discussed.

Jan 1, 1979

By J. M. Gomes

The Bureau of Mines investigated electrolytic techniques for preparing diborides of the group IV B metals. TiB2, ZrB2, and HfB2 were electro-deposited from their respective oxides dissolved in borate-chloride-cryolite electrolytes. Titanium diboride was also electrodeposited from rutile (Ti02) dissolved in a Na2,B4O7-Na2C03-Na3A1F6-NaC1 electrolyte at 1,050° C; 14 kW-hr were required to produce 1 pound of TiB2. Major impurities in the TiB2 produced in a 10-deposition cycle experiment, in weight-percent, were Al, 0.2; Cr, 0.3; Fe, 0.1; V, 0.3; C, 1.4; and 0, 1.0. Zirconium diboride was electro-deposited from zircon (ZrSiO4) dissolved in a Na2B407-NaOH-Na3A1F6-NaCl-NaF electrolyte at 1,050° C. The ZrB2 produced in a 10-deposition cycle experiment contained the following impurities in weight-percent; Fe, 0.1; Si, 0.5; C, 0.3; and 0, 0.6. Energy required to produce 1 pound of ZrB2 was 9.3 kW-hr.

Jan 1, 1975

By N. S. Dalal, X. Shi

"Electron spin resonance (ESR) spectroscopy has been employed to· examine the role of tetraperoxochromate( V) ions (Cro:-) and other Cr(V) species in the generation of hydroxyl (OH) radicals in the reaction of Cr(VI) with H2O 2 in biological media. In contrast to earlier suggestions, the present ESR studies using crystalline K3CrO8 as a source of Cro:- show that decomposition of Cro:- in water or in H2O 2 does not generate significant amounts of OH radicals. Addition of NADH to a solution containing Cro:- yields a Cr(V)-NADH complex, which readily reacts with H2O 2 to generate OH radicals. Similar results obtained from several other biological reductants, including vitamin B2 , indicate that a vacant coordination site on a Cr(V) complex facilitates its reaction with H2O 2 to generate ""OH radicals. We thus suggest that in biological media, reaction [3] instead of [1] or [2] is the major pathway for the OH radical generation: While the carcinogenic potential of Cr(Vl)-based compounds has been well established via epidemiologic and animal studies (1), the underlying biochemical mechanism is still not well understood (2). In a recent development, however, Kawanishi et al. (3) have reported that hydroxyl (OH)2 radicals might be the key species in the mechanism of Cr(VI) toxicity. As to the mechanism of the ""OH radical formation they suggest that Cr(VI) reacts with cellular hydrogen peroxide (H2O 2) to form the tetraperoxochromate(V) (Crog-) ions, which decompose to produce hydroxyl radicals. It was also suggested (3) that the ""OH radicals thus produced cause genotoxicity via DNA base modification and deoxyribose phosphate backbone alterations. More recently Aiyar et al. (4) reported the detection of OH radicals in the reaction of Cr(VI) with H2O 2 in biological media, including the reaction of ""OH radicals with deoxyguanosine to generate 8-hydroxydeoxyguanosine adducts, confirming that ""OH radicals could indeed play a significant role in the mechanism of Cr(VI) toxicity. However, the mechanism for the ""OH generation was not clarified, although the role of Crog- ions as possible precursors was mentioned, somewhat along the lines suggested by Kawanishi et al. (3). The possibility of the participation of Crog- in the ""OH generation has also been indicated by Sugiyama et al. (5), since they mention that vitamin B2 enhances the formation of""OH radicals in the reaction of Cr(VI) with H2O 2 because of the generation of Crog- in the reaction."

Jan 1, 1990

By J. F. Papp

The microstructures of a CF2Br2-inhibited methane flame and its uninhibited analog have been determined using molecular beam-mass spectrometry. The slightly lean flames were stabilized on a cooled porous plug burner at reduced pressure. Composition profiles of stable, intermediate, and radical species and temperature profiles were obtained. Comparisons of the uninhibited and inhibited flame profiles revealed the following inhibition effects; a shift of the primary reaction zone to higher temperatures, a higher maximum flame temperature, an increase in the CH3 concentration, and a reduction in the H2CO, H, 0, and OH concentrations. Kinetic analyses of the data yielded rate coefficients at flame temperatures for the reactions H + CH4 ? CH3 + H2, H + O2 ? OH + O, CO + OH ? CO2 + H, and CH3 + O ? H2CO + H. CF2Br2 is judged to decay by thermal decomposition and abstraction reactions.

Jan 1, 1981

By H. J. Heinen

A technique offering promise as a metallurgical processing sequence the recovery of molybdenum (Mo) from the sulfide mineral--molybdenite?was investigated. The method consists of two steps: (1) electrosynthesis of pure dimolybdenum carbide (Mo2C) from molybdenite (MoS2) and (2) interaction of Mo2C and molybdic oxide (MoO3) to produce pure molybdenum metal. Two molten salt systems were satisfactory for electrosynthesizing Mo2C. The first was a mixture of potassium chloride (KCl), potassium fluoride (KY), and sodium metasilicate (Na2SiO3), and the second consisted of sodium fluoride (NaF), KF, sodium tetraborate (Na2B4O7), and sodium carbonate (Na2CO3). Yields up to 0.42 gram of Mo2C per ampere-hour were obtained. The carbide, mixed with monitored amounts of MoO3, was converted to molybdenum metal of 99.9 percent purity by sintering at 1,500° C.

Jan 1, 1965

By Aarne Visnapuu

Dissociation and vaporization of gold chlorides and bromides were investigated by a static pressure method and by Knudsen cell mass spectrometer. Two distinct chlorine and three distinct bromine pressure-temperature relation-ships were observed for the respective salts. The chlorine pressures are attributed to the dissociation of Au2Cl6 and Au2C12, and the bromine pressures to the dissociation of Au2Br6, Au2Br4, and AU2Br2, These pressure-temperature relationships were used to calculate dissociation pressure equations, enthalpies, and entropies of dissociation for each salt. Mass analysis of the vapors over AU2Cls between 83° and 152° C confirmed the existence of gaseous AU2C16. Ionization potential of this molecule is 11.0±0.1 ev and enthalpy of vaporization is 28.l±2.0 kcal/mole. Mass analysis of the vapors over the gold bromides detected only Bra in the temperature range 15°-150° C.

Jan 1, 1971

By S. C. Rhoads

The Bureau of Mines is investigating low-chromium alloy substitutes for type 304 stainless steel (type 304 SS). The purpose of the research is to reduce the chromium content in austenitic stainless steels used for corrosion-resistant applications. Nine Fe-9Cr-12Ni alloys containing additions of 0 to 5 pct Mo, 0 to 2 pct V, and 0 to 2 pct Cu were selected for evaluation. All of the experimental alloys containing 5 pct Mo and an alloy containing 2Mo-2V-2Cu possessed structure and tensile strengths similar to those of type 304 SSe Alloys containing SMo-2V and SMo-2V-2Cu had ac-ceptable welding properties as measured by the Varestraint test. Alloys containing at least 2 pct Mo had cQrrosion resistance comparable to that of type 304 SS in solutions of nitric acid, phosphoric acid, acetic acid, and citric acid. In chlorides, all the experimental alloys were susceptible to localized corrosion and stress corrosion cracking similar to that of type 304 SSe The corrosion properties were established by weight-loss tests, electrochemical polarization tests, and stress-corrosion cracking tests. An Fe-9Cr-12Ni-SMo-2V alloy and an Fe-9Cr-12Ni-SMo-2V-2Cu alloy had a combination of welding properties, tensile properties, and corrosion resistances that were most comparable to those of 304 SS.

Jan 1, 1984

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 J. F. Shultz

The Bureau of Mines investigated the hydrogenation of carbon monoxide and carbon dioxide over Raney nickel catalyst and nitrided fused-iron catalyst using both a single-pass and a recycle system. Activation energy over Raney nickel catalyst is 29 to 32 kcal/mole for synthesis from either CO or CO2, Pressure dependence of the gas conversion is to the 0.3 power for synthesis from CO and to the 0.5 power for synthesis from CO2. Nitrided fused-iron catalysts were tested using high recycle rates and 3H2+lCO, 2H2+lCO, and 1H2+lCO feed gas at 21.4 atmospheres absolute pressure. The relative usage of hydrogen (moles H2 consumed per moles Ha+CO consumed) was larger than in corresponding single-pass tests, and the relative usage of hydrogen approached the feed gas ratio monotonically as conversion increased. Activation energy was found to be 12 or 13 kcal/mole fresh feed gases of 3H2+lCO or 2H2+lCO. For single-pass operation the activation energy under the same conditions was 19 to 21 kcal/mole.

Jan 1, 1967

By Edward J. Chuhta, Joseph E. Chilton, Robert J. Timko

in underground mines to measure worker exposure to various gases such as methane, carbon monoxide, and nitrogen dioxide (NO2). Even in relatively small concentrations, NO2 can produce harmful side effects in underground workers. Mines using equipment powered by diesel engines, carrying out explosive blasting operations, and performing extensive arc welding and/or cutting work will have measurable quantities of NO2 released by these processes. Workers in these areas often use gas monitors to warn of excessive gas concentrations and to help them determine when to increase ventilation air that will dilute these gases, thus minimizing exposures to this gas. Portable gas monitors, used to measure NO2 levels, must be calibrated before each use. Calibration is typically performed using a small portable pressurized cylinder containing a certified gas mixture. The certified NO2 standard mixture, usually 10 ppm NO2 concentration, is diluted with either air or nitrogen gas. To determine the stability of commercially available portable gas standards, two different cylinders containing NO2 in nominal 10-ppm concentrations were examined. One cylinder was diluted in air, the other, in nitrogen. Baseline NO2 mixtures were generated using a standard liquid NO2 permeation tube operated at a constant temperature. Final dilutions of the test gas mixtures were made with air or with nitrogen using a mass flow-controlled gas dilution system. This study showed that, when a permeation-type NO2 generator is used, the electrochemical sensors in portable NO2 monitors provide identical results for gas mixtures whether they are diluted with air or with nitrogen. Two different gas monitors, one with a two-electrode sensor and one with a three-electrode sensor, were used to measure gas concentrations in the two commercially available cylinders. One month after the cylinders were delivered, the NO2-in-nitrogen cylinder, stated to contain 10 ppm NO2, measured 8.13 ppm. The NO2-in-air cylinder, also stated to hold 10 ppm NO2, measured 6.88 ppm. Therefore, before using NO2 gas cylinders to calibrate monitors, it is recommended that their concentrations be verified either by manufacturer recertification or by comparing the stated cylinder gas concentrations to a laboratory-based permeation tube-generated standard.

Dec 1, 2005

By Peter C. Wood

This report describes research directed toward the preparation of chemical oxygen (02) sources which exhibited improved 02 storage and reaction characteristics when compared to potassium superoxide (KO2). The initial focus of the research was the preparation of calcium superoxide (Ca(02)2) by the disproportionation of calcium peroxide diperoxyhydrate. The Ca(02)2) was characterized by chemical, thermal, and x-ray analyses. Several methods for scaling up the Ca(02)2 synthesis process were studied. Next, the reactivity of Ca(02)2 toward humidified carbon dioxide (C02) was evaluated and was compare o that of K02 under flow-test conditions approximating those existing in portable breathing apparatus. The reactivities of mixtures of K02 and Ca(02)2 or lithium peroxide towards humidified CO2 were also studied. Finally, an analysis of two commercial, K02-based, self-contained self-rescuers was conducted to determine the potential weight and volume savings which would be possible if Ca(02)2 or a mixture of K02 and Ca(02)2 were used as a replacement for K02.

Jan 1, 1983

By C. J. Thompson

Two sulfur compounds--the 2,2,5-trimethyl- and the 2,2,5,5-tetramethyl derivatives of thiacyclopentane--were identified in Wilmington, Calif., crude oil, using microdesulfurization and gas-liquid chromtography techniques.

Jan 1, 1963

By Charles P. Lazzara

Concentration profiles of low-pressure, slightly lean CH4-02-Ar flames have been measured in situ for the following unstable species: oxygen atom, hydrogen atom, hydroxyl radical, methyl radical, and formyl radical. The observed maximum mole fractions were 2.0X10-2 for H, 1.1X10-2 for OH, and 0.8X10-2 for 0; the maxima occurred in the recombination zone. Methyl and formyl radicals have maximum mole fractions in the reaction zone of 2.2x10-3 and 6x10-5, respectively.

Jan 1, 1973

By R. O. Dannenberg

Exploratory research was conducted to ascertain the feasibility of recovering beryllium from Spor Mountain, Utah, ore by the sodium fluosilicate (Na2SiF6) method used industrially for processing beryl. Na2SiF6 requirements to form water-soluble salts of beryllium were determined for three different samples--two clayey ores containing 0.6 and 1.3 pct BeO, respectively, and a calcareous ore containing 0.6 pct BeO. The ores were sintered with Na2SiF6 at 750° C for 3 hours. About 80 pct of the beryllium was rendered water soluble by sintering the 0.6-pct BeO ores with 30 and 40 lb Na2SiF6 per lb BeO contained in clayey and calcareous ores, respectively. The higher grade 1.3-pct BeO clayey ore required only 20 lb Na2SiF6 per lb BeO to solubilize over 80 pet of the beryllium. As the 0.6-pct BeO clayey ore was possibly the most representative of the deposit as presently delineated, leach liquor prepared from this sample was treated to recover beryllium salts. About 60 pet of the beryllium contained in the ore was recovered as beryllium hydroxide, which then was calcined to yield a 99-pct BeO final product by means of the following operations: (1) Sintering with Na2SiF2, (2) leaching with water, (3) precipitating crude Be(OH)2 by adding NaOH, (4) filtering to separate the hydroxide from the NaF solution, (5) redissolving the crude Be(OH)2 in excess NaOH, (6) filtering to reject caustic-insoluble impurities, and finally (7) boiling the Na2BeO2 filtrate from (8) to precipitate pure Be(OH)2. Reagent consumption was 49 lb Na2SiF6 per lb BeO recovered and 17 lb NaOH per lb BeO.

Jan 1, 1963

By F. P. Haver

Because of increasing concern with air pollution, the Bureau of Mines has developed a hydrometallurgical procedure to obtain elemental sulfur from chalcopyrite (CuFeS2) by means of the following reaction: CuFeS2 + 3FeCl3 ? CuCl + 4FeCl2 + 2S. Under optimum conditions, 99.6 percent of the copper and 71.6 percent of the iron were extracted in 2 hours from a typical mill concentrate containing 75 percent CuFeS2 and 15 percent pyrite (FeS2). At the same time, 68.2 percent of the sulfur in the concentrate was oxidized to the elemental form. The leach was highly selective; gangue minerals, including pyrite, were not attacked, thus accounting for the relatively low recoveries of iron and sulfur. To obtain these results, the concentrate was ground to 98.9 percent minus 325 mesh, and 300 grams was treated with 1 liter of boiling ferric chloride (FeCl3) solution. The FeC13/CuFeS2 ratio was 2.7. Cement copper containing 99.9 percent copper was recovered from the leach solution by cementation on sponge iron. Excess iron, dissolved during leaching and cementation, was removed from the stripped solution by crystallization. Ferrous chloride (FeCl2?4H2O), obtained as a byproduct, was converted to high-purity ferric oxide (Fe203) and HCI by an oxidizing roast. The hydrochloric acid was then electrolyzed to obtain chlorine, which was used to regenerate the leach solution. The leach residue, which contained ~50 weight-percent elemental sulfur, was treated with an organic solvent to recover the sulfur and cyanided to reclaim gold and silver.

Jan 1, 1971

The objective of this handbook is to provide the inspector with guidance for recognizing hazards from inhalation contaminants in above ground work areas of underground and surface coal mining and processing facilities and evaluating these hazards by collecting samples or making field determinations and interpreting the analytical results. There are several portions of the handbook which should prove most useful to the inspectors. The names and locations of these portions are listed below: Survey Check List (Page 2-3) Rules for Determining if Sampling is Required (Page 2-1) List of Most Frequently Encountered Contaminants (Page 2-2) List of Candidate Contaminants and their Sampling Conditions (Table 2, Starting on page 2-5) Interpretation of Results (Page 2-16) Procedure for a, Health and Safety Inspection (Page 2-25) For obtaining information not available from the above mentioned portions of the handbook, the inspector is directed to the Table of Contents, the Glossary of Terms, and the List of Commercial Products Encountered in Surveys.

Jan 1, 1975

By F. S. Karn

Conditions necessary to obtain optimum yield of useful products when coal is rapidly heated to extreme temperatures by laser irradiation were determined by the Bureau of Mines. Product distribution and yield were investigated as functions of several variables. Low-rank coals with high-volatile matter gave highest total gas yields. Medium-rank coals gave the highest yields of H2 and CA and low-rank coals gave highest yields of CO and C02. Macerals gave gases of approximately the same composition, but the total gas yield increased in the order fusinite, micrinite, vitrinite, and exinite. Total gas and C2H2 yields varied inversely with particle size. The addition of nominally inert gases such as Ar, He, N2 increased yields of H2, C2H2, and total gas. Metals such as nickel and platinum had little influence on the rate of coal decomposition. Total gas yield increased with total energy of irradiation, and the ratio of C2H2-CH4 increased with concentration of energy. A study was also made of the irradiation temperature, and a material balance was calculated.

Jan 1, 1970