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By H. H. Heady

A naphtha obtained by destructive, recycle hydrogenation of crude shale oil, produced by gas-combustion retorting of Colorado oil shale, was found by the Bureau of Mines to contain 49.1 percent paraffins, 20.3 percent cycloparaffins, 7.8 percent olefins, and 22.8 percent aromatics. The naphtha contained only minor amounts of sulfur, nitrogen, and oxygen compounds. Compounds containing less than 5 carbon-atoms per molecule were removed by distillation before analysis. The paraffins where predominantly straight-chain compounds; n-Hexane was present in the largest quantity, and the other straight-chain paraffins decreased in amount as the molecular weight increased. The cycloparaffins, which contained both cyclopentanes and cyclohexanes, were evenly distributed throughout the boiling range. Although the naphtha had been produced by hydrogenation, it contained a small quantity of olefins. Straight-chain olefins with a terminal double bond comprised about two-thirds of these compounds. Among olefins with an internal double bond, those having trans configuration were present in three times the quantity of those in the cis form. In the aromatics all but one of the alkylbenzenes having nine or less carbon-atoms per molecule were identified; toluene was present in the greatest quantity. Only a few of the higher molecular-weight homologs were identified. The composition of the naphtha was computed from analyses of 105 narrow¬boiling distillation fractions. Volume, density, refractive indices, bromine number, and an ultraviolet spectrum were determined on each fraction. From these data the hydrocarbon-group composition of each fraction was estimated. A silica gel adsorption analysis was used to check the values of nearly one-third of the fraction calculated from physical-property data. Mass and infrared spectra were obtained on some fractions for identifying individual compounds or types of compounds, such as terminal olefins.

Jan 1, 1960

By E. G. King

Thermodynamic calculations involving the oxides of tungsten and molybdenum have been hampered by lack of accurate entropies and high temperature heat contents. This paper presents work by the Federal Bureau of Mines on new low-temperature heat-capacity data leading to the evaluation of the 298.15° K. entropies of tungsten dioxide and tungsten trioxide, as well as high-temperature heat contents (above 298.15° K.) of molybdenum dioxide, molybdenum tri-oxide, tungsten dioxide, and tungsten trioxide. Included are heats of fusion of the two trioxides. The heats of formation at 298.15° K. of these four oxides are tabulated as measured by Mah4 5/ of this laboratory. Included also are the 298.15° K. entropy of Mo02 measured by Kin 6/ of this laboratory, and that for Mo03 according to Kelley and King.7/ These basic data provide a consistent compilation from which to perform accurate thermodynamic calculations involving these compounds. No previous low-temperature- heat-capacity measurements have been reported for tungsten dioxide. Seltz, Dunkerley, and DeWitt8/ measured the low-temperature heat capacity of tungsten trioxide. The only previously-reported high-temperature heat-content measurements for any of the oxides were conducted by Cosgrove and Snyder,9/ who measured molybdenum trioxide to 1,300° K.

Jan 1, 1960

By W. M. Mark

This investigation was undertaken to develop methods to improve the quality of titanium sponge produced by the Bureau of Mines modification of the Kroll magnesium reduction process. Research revealed that by systematic elimination of detrimental impurities introduced with the raw materials and by improved handling and processing techniques, high-quality ductile titanium with a hardness of less than 110 B.h.n. (Brinell hardness number) can be produced consistently. This improvement was accomplished by helium (or argon) stripping of residual atmospheric and other dissolved gases from the titanic chloride, preliminary dehydration of crude titanium sponge, and careful regulation of the titanium tetrachloride (TiC14) feed rate to the reactors.

Jan 1, 1960

By J. P. Capp

This experiment, one of a series on underground gasification of coal, was an investigation by the Federal Bureau of Mines of hydraulic fracturing as a means of increasing the air acceptance of a coalbed to permit introducing combustion air and removing product gases. Specific objectives of the investigation included: (1) Fracturing a coalbed; (2) determining the distance the coal was physically affected; (3) ascertaining the effect of the fracture on air acceptance of the coalbed; and (4) gasifying the coal. The coal was fractured with a fluid consisting of 15,000 lb. of sand mixed with 10,000 gal. of fuel oil and 5,000 gal. of kerosine, injected at pressures up to 900 p.s.i.g. and rates up to 425 g.p.m. The oil served as the fracturing medium, and the sand as a propping agent to hold the fracture open. From the fracture point, (the place in the bed where the fluid was injected), the fracture extended 200 ft. or more along the face cleats, somewhat less along the butt. cleats, and was confined to the coalbed. At the fracture point, the bed accepted about 500 std. c.f.m. of air, which was an etghtyfold increase. Fracture effects were extensive, as airflow was noted from old mine workings and outcrops 600 to 800 ft. from the fracture point. It is probable the actual fracture was much less than 600 ft. and that normal coalbed permeability beyond the fracture limits was responsible for this flow. This indicated that effects of the fracture extended beyond the area of coal physically affected. Although no attempt was made to gasify coal more than 200 ft. away, these effects plus the natural permeability of the bed likely would permit combustion beyond the outer limit of the fracture. As these experiments continued for more than 2 years, and greater air acceptance due to the fracture was observed at the beginning of each test, it is apparent that the effects of the fracturing persist for a considerable time.

Jan 1, 1960

By R. M. Becker

THIS IS a progress report on a study of the application of statistical practice to mine and mineral sampling undertaken by the Federal Bureau of Mines to provide sound theoretical and practical data for use of the mineral engineering professions. One of the problems in mine sampling is determining the reliability of the results. For certain types of sampling data (random data) the reliability of the results can be stated mathematically. For other types of data there is no known means of quantitatively expressing reliability. In applying measures of reliability to a set of random data, some knowledge or assumption of the characteristics of the particular data is necessary. In many fields these characteristics are well known. However, in mining, where the data are in assays, these characteristics are not well known.

Jan 1, 1961

By L. J. Kane

Chemical processes using coal often require economical removal of dust from high-temperature gases. Laboratory-scale investigations by the Federal Bureau of Mines have shown that an aluminum silicate fiber is suitable for filtering dust from gases at 1,800° F. The effects of the bulk density of the filter, rate of gas-flow, concentration of dust in the filter, fiber diameter, depth of filter, and concentration of dust in the feed gas on removal efficiency, pressure drop, and capacity of the filter to hold dust were studied. The laboratory filters were difficult to construct because the fibers were longer than the tube diameter. This caused irregular distribution of fiber that permitted dust-laden gases to leak through channels developed in the filter. Leaks also formed between the filter and the tube wall, but this was minimized by improved filter design. However, edge leaks and leaks through channels in the filter probably would be insignificant in properly constructed filters of industrial size. As the concentration of dust in the filter increased, the efficiency of the low-density filters decreased, contrary to expectations, probably because a higher percentage of the dust passed through channels that developed in the filter. The efficiency of high-density filters, however, increased with the concentration of dust in the filter. Results indicate that loosely packed filters would have a longer life than tightly packed filters at the expense of efficiency. As regeneration or replacement of stationary filters is difficult and expensive, loose filters would be best for filtering gases containing much dust. Gases containing little dust may be cleaned with tightly packed filters to obtain higher efficiency. For either type of filter, precleaning with cyclone separators or other means is advisable.

Jan 1, 1960

By Henry H. Ginsberg

The effectiveness of 0.01 pct. molybdenum, as ammonium molybdate impregnated on coal, on the hydrogenation of a high-volatile bituminous C coal at 8,000 p.s.i.g. and 460° to 480° C. has been studied in a pilot plant by the Federal Bureau of Mines. Under these conditions, the Bureau obtained 98 to 99 pct. conversion5/ of coal to liquids and gases at throughputs of 29 to 101 lb. of m.a.f. coal per cubic foot of reaction space per hour. At 460° C. the indicated yield of oil ranged from 63 pct. (based on m.a.f. coal) at a throughput of 35 lb./c.f.h. (pounds per cubic foot per hour) to 68.5 pct. at a throughput of 58 lb./c.f.h., and the yield of gaseous hydro-carbons ranged from 25.5 to 19 pct. at the same throughputs. The maximum measured yield of oil boiling under 325° C. was 47 pct.

Jan 1, 1960

By Henry H. Ginsberg

The Federal Bureau of Mines made pilot plant investigations of the process requirements necessary to produce heavy fuel oil by the liquid-phase hydrogenation of bituminous coal. The investigation was carried out in three separate series of experiments. The first series studied the effect of temperature and contact time on product distribution at 3,500 p.s.i.g. and 420° to 480° C. in the presence of 0.1 wt.-pct../ stannous sulfide plus 0.05 wt.-pct. iodoform based on gross coal. As a result of increased contact times and temperatures, the conversion-6/ and yield of hydrocarbon gas increased, the viscosity of product oil decreased, and elimination of oxygen, nitrogen, and sulfur from coal increased. The yield of oil did not indicate any definite trend with changes in temperature and contact time. The yield of oil ranged from 76 to 85 pct. for Pittsburgh coal and from 60 to 85 pct. for Rock Springs coal. Asphaltenes in the product oil ranged from 17 to 38 pct. of the total oil for Pittsburgh coal and from 12 to 22 pct. for Rock Springs coal. Fuel oils meeting Bunker C or American Society for Testing Materials (ASTM) Grade 6 specifications were produced with Rock Springs coal at 0.2- to 1.0-hr. contact time and 440° to 480° C. and with Pittsburgh coal at 0.3- to 1.0-hr. contact time and 420° to 460° C. In the second series of experiments tin, nickel, iron, and zinc were evaluated as catalysts for the hydrogenation of Rock Springs coal to heavy fuel oil at 3,500 p.s.i.g. and 460° C. Using the apparent conversion of coal as criterion of catalyst activity, at a contact time of 0.45 hr. tin was the most effective catalyst; nickel and iron were nearly as effective, but the use of zinc resulted in much lower conversion. When the contact time was increased to 0.80 hr., the apparent conversion of coal was essentially the same for each of the catalysts. When the yield of oil boiling below 3550 C. was used as criterion of catalyst activity, at 0.45 hr. the order of activity was tin, iron, nickel, and zinc; at 0.80 hr. tin was far superior and the others were essentially equal. The product oils contained from 8 to 20 pct. asphaltenes.

Jan 1, 1960

By K. C. Dean

A semiquantitative test for the presence and identification of cesium and rubidium in rocks, clays, and mineral waters has been developed by the Bureau of Mines. The test can be used in the field, as a guide for the prospector, geologist, or mining engineer engaged in location or development [w]ork. It comprises two simple spot tests of a solution prepared from the [m]ineral sample. Phosphomolybdic acid, added to a drop of the test solution, [d]etects cesium, rubidium, and potassium in quantities as low as 60 parts per [m]illion. Silicomolybdic acid, added to a second drop of test solution, enables the operator to distinguish between cesium and/or rubidium and potassium. Test procedures, equipment requirements, and limitations of the method are described in this report. Cesium and rubidium were discovered in 1860 and 1861 by Bunsen and Kirchhoff with a spectroscope. The elements usually occur together, particularly in granite and granitic pegmatites. Rubidium does not occur as an essential constituent of any known mineral, yet it is found as a minor element in so many minerals that rubidium is 16th in abundance in the earth's crust. Cesium, which ranks as the 37th most abundant element, is the principal component of pollucite and a minor element in a wide variety of minerals.

Jan 1, 1960

By Alla D. Mah

No experimental heat-of-formation value has been reported in the literature for cerium sesquioxide. The heat of formation of bismuth sesquioxide has not been determined in recent years, and the older value was subject to large uncertainty. Accordingly, the heats of combustion of cerium sesquioxide and bismuth metal were measured by the Federal Bureau of Mines. The heats of formation were: ?H°298.15 = -427.01 ± 0.70 kcal. /mole for cerium sesquioxide and ?H°298.15 = -137.16 ± 0.30 kcal./mole for bismuth sesquioxide. The free energy of formation was estimated for cerium sesquioxide and accurately calculated for bismuth sesquioxide. The data were compared with values in the literature.

Jan 1, 1961

By E. C. Tarpley

The Federal Bureau of Mines has studied solvent extraction as a means of concentrating the mineral components in coal. Solubilities of a number of American coals were determined using abietic acid as a solvent. The effect of rank on solubility was investigated, and maximum solubility was found with coals of intermediate rank. Vitrinite is the most soluble petrographic component; fusinite, micrinitc, and exinite are nearly insoluble. Spore exines also have a low solubility. Abietic acid is a hydrogen donor and reduces pyrite to ferrous sulfide. Mild hydrogenation of high-molecular-weight fragments of the coal structure to those of lower molecular-weight probably contributes to the solvent action. Even where solubility of the coal substance exceeds 90 percent, contamination of the mineral matter with coal makes identification of the mineral components difficult. Further separation might be possible by the application of float and sink techniques to the residue. INTRODUCTION Work n the solvent extraction of coal is conducted to recover commercially useful products and to characterize coal;. and obtain information on their structure. Some coals, particularly those of low rank, contain waxes, resins, and humic acids which can be removed by solvent extraction and find varied industrial uses. In World War II, solvent extraction of coal was conducted on a commercial scale in Germany to obtain a low-ash feed material for hydrogenation and to produce electrodes carbon for the aluminum industry.4 5/

Jan 1, 1960

By R. V. Lundquist

Lime-soda sinters, made and processed for recovering alumina and soda, consisted of several types of compound structures differing from the ideal dicalcium silicate and sodium aluminate. Many or these compound structures were causes for low alumina recovery and contributed to the relation or leach slurries. Presence or free lime, whether in the sinter or released by hydrolysis of sinter compounds, contributed to relation of leach slurries. Free lime tends to establish the initial viscosity assumed by a leach slurry. Previous investigations by the Bureau of Mines (1, 4)4/ and by other laboratories (5) have demonstrated the technical applicability of the lime-soda sinter process to the recovery of alumina from aluminum silicate materials. The basic concept of the process is sintering aluminum silicate materials with limestone and soda ash for the production of dicalcium silicate and sodium aluminate and then extracting the sodium aluminate by leaching the sinter in causticized liquors. Alumina is precipitated from the pregnant liquors by carbonating with carbon dioxide. Reaction in the sintering operation may be represented by the following simplified equation: A1203?SiO + 2CaCO3 + Na2C03 = 2Ca0?SiO + Na20?Al203 + 3C02

Jan 1, 1960

By Charles K. Rose

The Cebolla Creek titaniferous iron deposits near Powderhorn in southern Gunnison County, Colo., were examined by the Federal Bureau of Mines as part of an overall program to investigate the Nation's titanium and iron resources. The deposits occur around the periphery of the Iron Hill stock, which underlies an area of about 12 square miles. Concentrations of magnetite, ilmenite, and perovskite arc localized along fractures in the pyroxenite stock. Mineralogical studies of composite surface samples collected in 1956 showed that most of the iron is present in ilmenite-bearing magnetite. Perovskite is the chief titanium mineral in the magnetite-rich and augite-rich types, and sphene is the principal titanium mineral in the placer material. The mica-rich rock contains approximately equal amounts of perovskite, ilmenite, and sphene.

Jan 1, 1960

By W. H. Oppelt

The Federal Bureau of Mines investigated combustion of lignite in domes-tic heating equipment to obtain information on equipment performance and to evaluate testing procedures. Three types of domestic heating equipment were tested, ranging from a hand-tilled, magazine-type space heater to a ram-type overfeed stoker. Lignite was readily burned in each of the three units under various test conditions. Burnoff rates determined by adding weighed charges to the magazine were found to be in error because of shrinkage of the lignite when only a portion of the magazine capacity was consumed during a test. More reliable burnoff rates could be determined by carbon-nitrogen balances. A hand-fired magazine-type space heater (Booker heater) was operated without the furnace attachment at efficiencies to 75 pct. One test series was run with minimum supervision under conditions encountered in actual household operation. No mechanical trouble was encountered.

Jan 1, 1960

By F. R. Cattoir

The Federal Bureau of Mines refined chromium from an aqueous electrolytic process in molten sodium chloride-chromium chloride electrolytes. Oxygen and nitrogen contents were reduced by a factor of 10 to 40, but most other impurities were little changed. The product usually contained a little more iron than the feed. Since iron was entering the bath from the iron pot and the graphite liner at a nearly constant rate, contamination of the chromium deposits by it was more serious at low currents and deposition rates. A few runs in an iron cell with a nickel liner yielded chromium containing one half as much iron as the feed, but up to 1.5 pct. nickel. In all cases the anode feed lay in the bottom of the container, which itself was used as the anode connection. With a 12-in. cell, variations in applied voltage from 0.05 to 1.5, in current from less than 10 to over 100 a., and in initial cathode current densities from less than 100 to over 2,000 a./sq.ft. had little or no effect upon the analysis of the metal produced) except for iron content. Changes in bath analysis from 3 to 11 pct. chromium were also without effect. These changes did bring about large differences in the physical forms of the crystals obtained. The thick heavy crystals produced at low voltage and current contained voids which made them difficult to leach free of chlorides. Easiest to leach were the thin leaf-like crystals obtained at around 1 v.

Jan 1, 1960

By R. V. Lundquist

A method was developed by the Federal Bureau of Mines for evaluating viscosity data from slurries obtained in leaching sinters from the lime soda sinter process for extracting alumina from aluminous silicates. The logarithm of the viscosity was observed to be a linear function with time. The slope of the plotted line provides a means for evaluating viscosity behavior in a lime soda sinter blurry and also a means for comparing gelation characteristics directly with other variables in the lime soda sinter process. This report presents one aspect of a continuing study by the Bureau of Mines on methods for treating siliceous aluminum ores. It is one of the many programs of the Bureau concerned with conservation, development, and use of our domestic minerals resources. Previous investigations of lime soda processes, both by the Bureau4-7/ and industrial concerns, have demonstrated that sintered materials containing CaO, Na2O, A1203, and S102 in various combinations exhibit a tendency to gel or set when mixed with water or other extraction solutions. Gelling prevents satisfactory recovery of alumina and in extreme cases prevents operation of an extraction plant.

Jan 1, 1960

By S. L. Ausmus

The work covered in this report is a continuation of an earlier feasibility study by the Federal Bureau of Mines and points out improvements in the skull-melting method for casting reactive metals such as titanium, zirconium, and hafnium. Machined graphite molds with laminated sections can be reused many times. Large tube sections can be produced by spin casting. Graphite powder is the best expendable mold material, but binders for this use must be compounded carefully. The effects of current and furnace atmosphere on the dependent variables of the casting technique are shown. Because of developments in casting technology for titanium which eliminate the basic problems of melting and pouring the metal, opportunities for improvement in the method have increased. The mold material and gate and riser configurations require particular attention. The limits of application of the casting method have yet to be defined. New knowledge in anyone of these areas could result in marked improvements and simplifications in casting methods.

Jan 1, 1960

By Thomas J. Blalock

The volumetric determination of uranium according to the method of Sill and Peterson (6),3/ which uses cerate oxidimetry after the separation of interferences such as sulfides and cupferrates, has been used for some time by the Bureau of Mines and gives satisfactory results for many of the samples tested. However, in those instances where the uranium content did not exceed a few tenths of 1 percent and iron was present in the range of 10 to 40 percent (as Fe203),4/ the method was cumbersome and unreliable. The need for a more accurate procedure for the determination of small amounts of uranium in the presence of large amounts of iron, such as in shale or black sands, prompted this investigation. The Bureau desired that materials containing as little as 60 p.p.m. of uranium be assayed within reasonable limits of accuracy. One of the primary aims of this work has been to eliminate, as far as possible, the necessity for repeated cup ferron extractions.

Jan 1, 1960

By H. L. Gibbs

Many factors contributed to the decision to build a radiochemical laboratory at the Salt Lake City Metallurgy Research Center to investigate the application of radioactive isotopes and chemical compounds in extractive metallurgy. These reasons included the notable success achieved in biological sciences with radioisotopes, the development of reliable instruments and methods for identifying the isotopes and measuring their activities, and the commercial availability of radioisotopes in a variety of forms and known activities. The paramount reason, however, was the realization that better methods were needed for guiding and quantifying research to resolve the complex extractive metallurgy problems under study at the Research Center. This is the first of a series of reports describing the application of radioisotopes and radioactivity techniques in extractive metallurgy. The report includes a discussion of licensing and safety requirements, a general description of the laboratory and the methods used, a definition of the nature and scope of the research program, and a synopsis of the more important problems studied. Subsequent reports will concern radioactive techniques for solving specific problems in mineral dressing, hydrometallurgy, and pyrometallurgy.

Jan 1, 1960

By Walter Kawa

In connection with its research in producing synthetic liquid fuels from coal, the Federal Bureau of Mines studied reactions of iron and iron compounds with hydrogen and hydrogen sulfide in batch autoclaves. The Bureau hoped to gain indirect evidence regarding the chemical changes that iron catalysts undergo when they are used in the hydrogenation of coal. The information obtained may be helpful in identifying the active form or forms of iron catalysts. At 450° C., with hydrogen at hundreds of atmospheres and hydrogen sulfide at 1 or 2 atmospheres, the thermodynamically stable form of iron is ferrous sulfide in the case of the metal, magnetite, ferric oxide, ferrous sulfate, ferrous oxalate, or the chlorides of iron. However, complete conversion to ferrous sulfide was not achieved at temperatures of 400° to 500° C. for kinetic reasons. Extensive sulfiding of iron, magnetite, ferric oxide, and ferrous oxalate occurred below 400° C., and some conversion of ferrous sulfate to ferrous sulfide occurred at 400° C. In the hydrogenation of coal, ferrous sulfide is the form of iron likely to be available for heterogeneous catalysis when starting with the metal, oxide, sulfate, or oxalate.

Jan 1, 1960