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By K. K. Kershner

This report describes an investigation by the Bureau of Mines designed to provide background data for extending and improving the applications of chlorine metallurgy in extracting metals from ores. Optimum conditions are given tor chloridizing galena, sphalerite, and chalcocite by contact with chlorine gas. Petrographic and chemical analyses of the sulfides used in the experiments are listed. Graphs are furnished showing the extent of chloridization of each metal sulfide over the temperature range of the observations. In each case, the first tests were made with the reaction chamber at room temperature. This temperature was increased by regular increments in succeeding tests until the temperature was reached at which quantitative conversion of the sulfide to chloride was observed. The data are also plotted for screen-size fractions of the sulfide minerals investigated. Data show that the extent of metal chloride formation was affected by chloridization time, particle size of the sample, and usually, the temperature of the reaction chamber. At 300° to 400° C. an anomaly was noted for both galena and sphalerite. The temperature at which this anomaly was observed varied according to the particle size of the mineral. Comparisons are made between the chloridizing characteristics of the mineral sulfides and their chemically prepared counterparts.

Jan 1, 1961

By R. J. Leary

Significant improvements in surface conditions or mechanical properties of steels have been attributed by several investigators to ladle additions of small quantities of rare-earth metals or their oxides. To investigate systematically these effects in wrought and in cast plain carbon and alloy mechanical steels containing approximately 0.35 percent carbon, heats of four representative compositions were melted by the Bureau of Mines in a 4-ton open-hearth furnace. Each heat was cast into three sets of ingots to exemplify respectively, treatments with (1) rare-earth metals, (2) rare-earth metal oxides, and (3) an untreated set as a control. The development of melting, casting and rolling practices is described and discussed. Lance injection of oxygen shortly after melt raised the temperature of the metal immediately as much as 500° F., principally because mechanical agitation exposed the high-carbon metal to the flame and furnace root. An exceptional degree of superheat in the metal at the termination of the refining period was attributed to oxygen injection during the refining period. Bath temperatures higher than industrial practice were permitted by the all-basic furnace lining. Rates of carbon elimination as high as 0.036 percent carbon per minute were achieved by oxygen injections.

Jan 1, 1961

By Joseph Grumer

An instrumented spherical vessel has been used for many years to study laminar combustion waves. Concurrent measurements of flame speed and pressure-rise rates have led to evaluations of burning velocities, the pressure dependence of the burning velocity, and the expansion ratios of the gases passing through the combustion wave. For the most part, these studies have involved flames initially at atmospheric or subatmospheric pressure. The old spherical vessel used by the Bureau of Mines was not designed for use at elevated pressures. Moreover, being made of wrought iron, it was susceptible enough to corrosion to prohibit its use with many combustible mixtures that figure in industrial research. In mid-1956, under sponsorship of the Office of Naval Research, the Bureau undertook the development of a stainless steel spherical vessel capable of withstanding explosions of gaseous mixtures at initial pressures as high as 20 atm. and initial temperatures as high as 250° C. The design called for a double array (cross) of closely spaced small windows for observation of the flame as it traversed the vessel and a piezoelectric transducer to measure concurrently pressure-rise rates. Because no commercial contractor was willing to bid on the construction of such a vessel, it was built at the Bureau's Bruceton machine shop.7

Jan 1, 1961

By Willard L. Hunter

The Bureau of Mines smelted samples of chromite ore and concentrate from the General Services Administration (GSA) purchasing depot at Grants Pass, Oreg., in a submerged-arc furnace to establish smelting conditions and the energy requirement to produce high-carbon ferrochromium. Raw material, in the form of ore, flux, and reductant, and electrical energy are available on the Pacific coast to smelt the chromite. The concentrate can be smelted without prior agglomeration by employing hogged wood (wood chips) as a major portion of the reductant. The energy requirement is relatively low, about 3,960 kw.-hr. per ton of alloy. The ferrochromium produced will contain about 60 percent chromium. In addition to the smelting data, a statistical summary of the grade and amount of chromite purchased during the stockpile program and estimated chromite reserves and production volume are given. It is estimated that 632,000 tons of Cr203 contained in chromite of all grades is available in the western coastal States. Of this total there appears to be sufficient metallurgical-grade and beneficiable ore to sustain a smelting operation for 25 years at a consuming rate of 25,000 tons a year, utilizing material comparable to that delivered to the Government stockpile.

Jan 1, 1961

By T. N. McVay

The Bureau of Mines has developed a field test for detecting the presence of columbium in a variety of minerals containing the clement. The test consists of fusing the mineral or rock powder with potassium pyrosulfate in a porcelain crucible, digesting the melt with hot dilute hydrochloric acid to release the columbium oxide (Cb205), and subsequently reducing the columbium oxide to a lower oxide by adding tin, which gives a blue color to the contents of the crucible. The method will detect 1 percent of contained columbium oxide (Cb205) in a mineral sample provided no tungsten is present. If a mineral containing appreciable titanium is test,-!d in the same manner, the solution in the crucible becomes violet. In the presence of columbium, titanium at first causes a violet coloration of the solution, which after a few minutes is masked by the stronger blue of the reduced columbium oxide. Although tantalum oxide (Ta205) does not interfere with the columbium test, tungsten gives a blue color that is indistinguishable from the color obtained with columbium. A simple method is available to detect the presence of columbium in the absence of tungsten, but when the presence of tungsten is suspected, the sample must be subjected to somewhat more elaborate chemical tests to determine the presence or absence of columbium. Although these latter tests can be made in the field, several steps are involved that arc best performed in the laboratory with simple equipment.

Jan 1, 1962

By F. E. Brantley

Research was undertaken by the Bureau of Mines to assess the technical feasibility of smelting cement-copper precipitate in an electric furnace to produce commercial-grade copper. The blister-grade copper produced in smelting was refined by gaseous oxidation and reduction methods to rive a product equal in quality to fire-refined copper. The cement copper used in the study was typical of the material produced in commercial operations. The sample product was received in a partially oxidized state and analyzed 77.5 percent Cu, 3.4 percent Fe, 0.8 percent Pb, 0.05 percent Ni, 0.6 percent Sn, and 0.9 percent S. Smelting tests were made on the precipitate using laboratory-size induction and electric-arc furnaces. Three types of furnace linings were tested during, the investigation: Carbon, including graphite; clay-graphite; and silicon carbide. Although all proved satisfactory, either carbon or graphite was preferred because of their superior refractory properties and low permeability to molten copper. Copper recoveries in the induction and arc smelting tests averaged 92 percent in commercial-grade metal assaying 99.8 percent copper. Refining the molten copper by oxidation and gaseous reduction or by chlorine lancing increased the purity to plus 99.9 percent.

Jan 1, 1961

By R. Barany

This report contains the results of experimental work conducted by the Bureau of Mines to obtain the heats of formation at 298.15° K. of analcite, dehydrated analcite, lawsonite, anorthite, hexagonal anorthite, and leonhardite. Thermodynamic data for these minerals have applications in ceramics, extractive metallurgy, and particularly in geochemistry. Except for data on anorthite, no previous similar data existed. The present results will be a substantial aid in deriving the temperature-pressure-equilibrium relationships among these minerals. The heats of formation were determined by solution calorimetry, with hydrofluoric acid as the reaction medium. The results were expressed both in terms of the constituent oxides and in terms of the constituent elements. The heat of formation data were combined with related entropy values to obtain the free energies of formation at 298.15° K.

Jan 1, 1962

By K. K. Kelley

Thermodynamics data for silicates have applications in the fields of extractive metallurgy, ceramics, and geochemistry. To facilitate these applications, up-to-date tables of heats and free energies of formation are needed. It is the purpose of this report to supply such tables for anhydrous silicates. During the last 15 years the heats of formation of a substantial number of anhydrous silicates have been reliably determined at or near room temperature. This resulted from the development (first by the Bureau of Mines and later by the Geophysical Laboratory of the Carnegie Institution of Washington, by the Institute of Geology of the University of Helsinki, Finland, and by the Department of Geology of the University of Chicago) of accurate solution calorimeters, employing hydrofluoric acid as the reaction medium. Specific references to work of these laboratories will be made in the next section of this report. Also, entropy data at 298.150 K. and high-temperature heat-content values are available for many of these silicates, mainly owing to work of the Bureau of Mines. Most of these entropy and heat-content data have been compiled in Bureau of Mines Bulletins (13, 15).3

Jan 1, 1962

By M. D. Schlesinger

As part of the development of processes for producing synthetic fuels from coal, the Bureau of Mines prepared a special jet fuel in a pilot plant for evaluation by the Air Force. This jet fuel had all the required physical properties, including the important specifications of high heating value and high density. However, the finished fuel did not pass the stability test specified by the Air Force and conducted by the Southwest Research Institute in a high-temperature research coker. The cause for this instability is being investigated because pure compounds of the type identified in this fuel are known to be stable. The tar acid oil used was a 230° to 300° C. fraction of low-temperature tar obtained by carbonization of a West Virginia bituminous coal in the pilot plant of the Consolidation Coal Co. Both the desulfurization at 400° C. and saturation at 300" C. were done in the vapor phase at 2,500 p.s.i.g. After catalytic treatment and distillation the final jet fuel had a boiling range of 194° to 247° C., a net heating value of 18,420 B.t.u./lb. and a specific gravity of 0.8463 60° F./60° F. It also had u pour point below -62° C., and at 0° C. its viscosity was 4.5 cs. The oil was virtually all bicyclic, 41 pct. noncondensed and 56 pct. condensed.

Jan 1, 1961

A spectrographic procedure applicable to the semiquantitative determination of 29 elements in tungsten is presented. The method is designed to give estimates of impurity concentrations up to 500 p.p.m. Limits of detectability range from 0.3 p.p.m. for the more sensitive elements to 100 p.p.m. for the less sensitive ones. Tungsten metal samples varying in particle size from minus 300-to 30-mesh are excited in the presence of 5 percent germanium with a direct current arc. Germanium acts to stabilize the arc, minimizes the volatilization of tungsten, and serves as an efficient carrier to sweep impurities from the tungsten into the excitation zone. Curves are presented that show the volatilization behavior of germanium, tungsten, and impurities in tungsten at different concentration levels. Data obtained were used as guides in establishing the method of analysis. In the absence of established reliable analytical procedures for determining many impurities in tungsten in the parts per million concentration range, the spectrographic method described here should prove to be helpful in evaluating high-purity tungsten.

Jan 1, 1961

By W. S. Landers

In contrast to the large fund of information available on the carbonizing properties of Eastern U.S. coals, the experimental data available for most Western U.S. and foreign coals are meager. To supply some self-consistent data, the Bureau of Mines conducted 220 low-temperature carbonization assay tests at 500° C. in a laboratory-scale carbonization apparatus. The results are included in this report. The U.S. coals tested are from Alaska, Arizona, Colorado, Illinois, Montana, New Mexico, North Dakota, Pennsylvania, Ohio, Texas, Utah, and Wyoming. Assays were also made on coals from Canada, Ecuador, France, Greece, India, Mexico, the Philippine Islands, Thailand, and Yugoslavia. In addition, one assay of pine sawdust and one assay of a peat from Ireland are reported. Prediction equations were developed relating the yield of products of carbonization obtained at 500° C. in the assay unit to the proximate and ultimate analyses of the coals. The equations for predicting the yields of tar plus light oil, char, and gas, and the heating value of the gas, are considered good, each equation having a multiple correlation coefficient of 0.90 or higher. The equation predicting volume of gas obtained upon carbonization is considered as fair, with a multiple correlation coefficient of 0.84. A reproducibility study of the assay made on 10 replicate samples of a subbituminous coal indicated that the standard deviation of the individual products was 0.31 percent or less.

Jan 1, 1961

By M. R. Geer

The washability examination of a coal establishes the quality of the product that could be prepared by mechanical cleaning, shows how much impurity would have to be eliminated to attain a particular quality of product, indicates what type of cleaning process would be suitable, and tells whether the coal could be cleaned efficiently, The coal-preparation laboratories of the Bureau of Mines make washability examinations of coal for a variety of purposes. Sometimes these examinations are made as an integral part of research conducted on coal-washing problems. Occasionally they are made on coals mined on Government-owned land or on coals destined for use in Government installations. Often they are made on coals from new fields or new beds in existing fields to help establish the characteristics of the Nation's coal reserves. Whatever the original reason for doing the work, the results often are useful later in evaluating deposits or in the design of cleaning plants. Publication of the results of such studies provides for the widest possible usefulness. This report brings together the results of washability examinations made on 1 coal each from Oregon and Idaho, 2 from Wyoming, 5 from Utah, and 11 from Washington. Material of this nature is inherently difficult to summarize. Some of the coals are so clean} despite full-scam mechanical mining, that they could not be improved materially by washing; others present some of the most difficult preparation problems found in the country.

Jan 1, 1961

By W. A. Cole

This report covers the preliminary phase of an investigation of clays, shales, and certain rocks in Wisconsin to determine the feasibility of processing lightweight aggregate in the State. The study was extended to include rotary-kiln testing of a limited number of shale samples, and to an appraisal of the Maquoketa shale resources in eastern Wisconsin. A total of 45 samples of clays, shales, and other argillaceous rocks of Wisconsin were tested. The lower Maquoketa shale is the only material found to date that offers possibilities as a source of material that can be processed in a rotary kiln for lightweight aggregate. Bedrock occurrences of the Maquoketa shale are found in the eastern and southwestern parts of the State. The populous southeastern region of Wisconsin presents a large potential marketing area for lightweight aggregate. For this reason special study was directed to the Maquoketa shale in the eastern district.

Jan 1, 1961

By W. M. Dressel

A simple field test for detecting the presence of germanium in rocks, coals, and flue dust has been developed by the Bureau of Mines. The method consists of dissolving germanium from the samples by either acid or fusion treatment methods, adding a few drops of hematein or phenylfluorone dye, and extracting the resulting colored complex with carbon tetrachloride. INTRODUCTION Germanium is obtained commercially as a byproduct of zinc production, as a coproduct of base-metal refining from germanium-bearing mineral, and as a recovered product from the ash of some coals. The growing use of germanium in the electronics industry has increased demand for this semiconducting metal to the extent that an intensive search for new sources of supply is necessary.

Jan 1, 1962

By Paul S. Lewis

Bench-scale experiment~ by the Bureau of Mines showed the gross effect of retention times ranging from 0.1 to 14.5 minutes on the conversion of high-volatile C bituminous coal to liquids and gases. The uncatalyzed coal was hydrogenated at 400°, 450°, and 538° C. and 500, 1,000, and 2,000 p.s.i.g. The percent coal conversion increased rapidly during the initial 3 minutes and asymptotically approached a maximum within 7 minutes at all conditions. Reasonably good correlations of coal conversion with time, pressure, and temperature were obtained. Temperatures up to 900° C. and retention times of about 1 minute are recommended for future experiments with the objective of producing only gaseous hydrocarbons and partially devolatilized coal suitable for use as solid fuel. The reactor contained 13 semicircular ledges, and the retention time was controlled by the rotation of scrapers which swept the coal from ledge to ledge. Only coal feeds that did not adhere to the internal mechanism could be used.

Jan 1, 1961

By T. E. Gray

This report describes the preparation characteristics of the significant coalbeds in Boone County, W. Va., as determined by the Bureau of Mines. It is one of a series describing the coals suitable for producing metallurgical coke, either as mined or after beneficiation. Over 6.3 million tons of coal was produced in Boone County, W. Va., in 1959, of which almost 5.5 million tons was mechanically cleaned in eight preparation plants. On December 31, 1959, it was estimated that almost 8 billion tons of coal remained in the county in beds 24 inches or more in thickness. Thirteen samples were collected from nine coalbeds and washability tests were made on these samples.

Jan 1, 1961

By William G. Gruzenaky

The separation of yttrium and the individual rare-earth elements (lanthanons) from mixtures in which they occur has been a difficult problem through-out the years. Because of the increased interest in the various uses of these metals, the economy of their production may become of great importance. Studies relative to this problem, undertaken at the Federal Bureau of Mines Albany Metallurgy Research Center, resulted in the development of a solvent extraction method by which yttrium can be separated from the rare-earth metals. A separation factor of 10.93 was obtained between yttrium and cerium from a single-stage extraction, and a factor of 1.78 was obtained between yttrium and erbium from a multistage system. The valuable metals were extracted from euxenite by caustic soda fusion or by chlorination, and several separation methods were investigated. Partial separation of the yttrium and rare-earth element fraction was made by chemical methods and by solvent extraction. Thermal decomposition of aqueous rare-earth nitrates or selective ignition of yttrium and rare-earth oxalates yielded a fraction enriched in cerium. A fraction enriched in the light rare-earth elements resulted from a double sulfate precipitation, whereas a potassium ferrocyanide pr cipitation yielded a fraction enriched in yttrium. Precipitation with dimethyl phosphate yielded a fraction enriched in yttrium and heavy rare-earth elements. Enriched fractions were obtained with several solvent extraction systems. A system consisting of rare-earth nitrates, nitric acid, and tri-n-butylamine-3 methyl-2-butanone favored the separation of yttrium from the heavy as well as from the light rare-earth elements.

Jan 1, 1961

By S. J. Gasior

Pilot plant studies showed the technical feasibility of fluidized-bed operation for producing hydrogen and synthesis gas by the steam-iron process. A mixture of iron and iron oxide from 20-to 100-mesh was partially reduced with a simulated producer gas and then oxidized with steam and/or carbon dioxide. Results of tests show the effects of pressure, temperature, bed height, gas-to-solids ratio, type of iron oxide, and composition of gas on the gas and solids conversions during reduction and oxidation. A baffled free-fall solids system was also found operable. The short residence time of about 5 seconds limited conversion of the solids.

Jan 1, 1961

By J. B. Gayle

Numerous investigators have studied the addition of inert4 substances to coking blends. Generally, the results have yielded trends applicable only to the particular coals and inerts studied. Recently, somewhat more general results were obtained for cokes produced from blends containing added inerts, using the sole-heated oven. The present investigation represents an extension of this work to include a wider range of inerts and to determine the applicability of the various conclusions to cokes produced with the Tuscaloosa oven. The results indicated that an increase in dry-coal charge density of 1 pound per cubic foot (p.c.f.) caused a corresponding change in the hardness (1/4-inch tumbler index) of Tuscaloosa oven cokes of 0.9 percentage points. This value compares favorably with the value of 0.7 determined previously for the sole-heated oven and Bureau of Mines-American Gas Association (BM-AGA) retort.

Jan 1, 1961

By W. P. Haynes

The Bureau of Mines has been studying a modified steam-iron process using coal-derived producer gas for making either hydrogen plus carbon monoxide or methane. To provide a guide for this experimental study, compositions of equilibrium product gases for the reaction of steam plus carbon dioxide with iron were calculated and are discussed in this report. The calculations, which are described in this report, are based on thermodynamic data in the literature and cover temperatures from 800° to 1,300° K., pressures from 1 to 30 atmospheres, and hydrogen-to-carbon atomic ratios in the gas of 4 to 12. The equilibrium gas compositions are discussed in regard to making hydro-gen, carbon monoxide, and methane in the oxidation step of the modified steam-iron process. From the viewpoint of thermodynamics alone, assuming the reactions reach equilibrium, the discussion considers the effects of temperature, pressure, and composition of feed gas upon the composition of the product gas, the degree of oxidation of the iron, and the possible deposition of carbon. The results indicated the following: (1) Nearly all the carbon can be converted to methane at low temperatures (800° to 900° K.) and high pressures (over 20 atmospheres); (2) to obtain high yields of synthesis gas, high temperatures are required. For example, at 30 atmospheres, a temperature over 1,200° K. is required to convert 60 percent of the steam plus carbon dioxide to hydrogen plus carbon monoxide. Lower temperatures may be used at lower pressures) (3) oxidation of the iron increases with increasing pressure and decreases with increasing temperature; and (4) process conditions favoring carbon deposition were found within the range of variables studied, but it is thermodynamically possible to operate the oxidation process with steam and carbon dioxide outside this range of carbon deposition.

Jan 1, 1961