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By A. J. Forney

Recent experiments used catalysts of plate assemblies in synthesizing high-Btu gas and gasoline indirectly from coal. A gas with a heating value of 925 to 943 Bt-: per cubic foot has been prod u la the hot-gas-recycle pilot plant from synthesis gas (3H2+100) with lathe turnings used as catalyst in the first reactor, and assemblies of parallel sprayed plats of nickel in the second. Solid plates made of Raney nickel, and steel and aluminum plates sprayed with Raney nickel or nickel oxide were tested. Those catalysts had very low resistance to gas flow; 90 percent lower than nickel granules used in previous experiments. In a single stage of synthesis thee nickel plates were only partially successful. Although the heating values of the product gas ranged from 856 to 941 Btu per cubic foot, the carbon monoxide content of he gas was above 0.1 percent. Both steel and wrought turnings were tested in single-stage synthesis, but the conversion of hydrogen and carbon monoxide was too low to attain the desired heating value of 900 Btu per cubic foot in the product gas. Assemblies of plates thermally sprayed with fusel iron were tried in an experiment to make gasoline. A gasoline yield of 52 percent (of the hydro¬carbons produced) was obtained using a 1H2-10O feed These sprayed assemblies were in service for 1,500 hours, the longest that this type of catalyst has been used. When a second reactor containing Raney nickel catalyst was added in series with the first reactor, complete utilization of the feed gas was obtained because in addition to the liquid product, a high-Btu gas with a heating value of 800 Btu per cubic foot was made.

Jan 1, 1965

By C. C. Popoff

This report reviews the phosphate deposits, mines, and industry, and prospects in 10 districts covering most of the Montana phosphate field. These districts are discussed individually, and an evaluation of the resources and potential of each is presented. Phosphate rock produced from underground mines in the Garrison district is shipped to Canada for processing to fertilizers, utilized locally for production of animal feed supplement, and pulverized and sold for direct application to the soil. Production from the Melrose district is shipped to Silver Bow and processed to elemental phosphorus. The Maxville-Philipsburg district is destined to become a major producer with the development of the Douglas Creek mine and beneficiation plant by Montana Phosphate Products Co. Montana ranks fourth after Florida, Tennessee, and Idaho in total annual production in the United States. Production him increased from about 60,000 long tons of acid-grade phosphate rock in 1940 to more than 660,000 tons of acid-, beneficiation-, and furnace-grade ore in 1961. Montana has the second largest potential resources in the Western field; in the area south of Butte there are approximately 1.2 billion tons of phosphate rock (+18 to +31 pct P2O5) available above and within 100 feet below entry level; and in the northern part of the field there are about 67.6 million tons available above entry level. In contrast to Idaho, most of the phosphate deposits in Montana are best suited to underground mining.

Jan 1, 1965

By A. W. Henderson

This investigation was performed to develop chlorination methods for extracting tungsten from scheelite and from an ore concentrate containing a mixture of scheelite and wolframite. On a laboratory scale with proper temperature control using elemental chlorine, over 90 percent extraction of tungsten is achieved. Carbon and sulfur dioxide were studied as reducing agents. The effects of salts such as calcium fluoride and sodium chloride were studied as additives to increase extraction and to reduce impurities in the volatile tungsten chloride product. Sodium chloride reacts with ferric chloride to form a nonvolatile double salt; whereas the chlorides and oxychlorides of tungsten are volatile and consequently condense free of iron. Separation of tungsten from molybdenum from an equal molar mixture was successful by fractionally distilling the oxygen-free chlorides and by selectively condensing the oxychlorides. Yields of 60 and 80 percent, respectively, were achieved for separating the less volatile tungsten chlorides containing less than 0.5 percent molybdenum.

Jan 1, 1965

By John W. Sweeney

Shales and clays from Illinois were sampled, tested, and evaluated to determine feasibility of producing lightweight aggregate by rotary-kiln methods. Sampling procedures and the 1 ,,,y of the Pennsylvanian shale units are discussed. Chemical, X-ray spectrographic and X-ray petrographic analyses were run on the samples to determine if a correlation existed between chemical mineralogic composition and expansion. Preliminary expansion testing was conducted in a muffle furnace. Rotary-kiln tests were conducted in a 16- inch by 14-foot rotary kiln. The weight of the aggregate ranged from 27 to 59 pounds per cubic foot. Concrete cubes employing the aggregate were tested to determine the qualities of the concrete. Compressive strength of the concrete using the 7-bag of cement cement per cubic yard mix, after autoclave curing for 6 hours, ranged from 2,950 to 6,750 psi. No correlation was found between the chemical, X-ray spectrographic, and X-ray and petrographic analyses and expansion, Sixteen samples made suitable lightweight aggregates in the laboratory rotary kiln. The expansion temperature range of eight of the samples was extremely narrow, and difficulties would probably be encountered in processing these materials commercially.

Jan 1, 1965

By G. W. Birge

Fifteen coal samples, representing the Winifrede, Chilton, Alma, No. 2 Gas, Powellton, Eagle, Douglas, Sewell, Beckley, Pocahontas No.4, and Pocahontas No.3 beds in Wyoming County, and five samples, representing the Fire Creek, Pocahontas No.6, and Pocahontas No.3 beds in Mercer County, W. Va., were carbonized at 9000 C by the Bureau of Mines-American Gas Association (BM-AGA) method, and yields of products and physical properties of cokes were determined. Expansion characteristics of the majority of samples were determined in the Bureau of Mines sole-heated oven. Chemical analyses and agglutinating values were determined for all coals. The coals were mostly strongly coking and low in ash and sulfur content. Dry, mineral-matter-free fixed-carbon content of the Wyoming County coals ranged from 63.0 to 83.4 percent. The Mercer County samples were all low volatile in rank. Yields of carbonization products were generally in accord with yields from similar rank coals of the Appalachian region. Because of their expanding tendencies, most of the medium-and low-volatile coals would require blending with lower rank coal for normal coke production.

Jan 1, 1965

By Stephan Stecura

Crystallographic modifications and kinetics of solid-state phase trans-formations were determined for five rare-earth" sesquioxides--La2O3, Nd2O3, Sm2O3, Eu2O3, and Gd2O3. Oxides used for crystal modification studies were prepared by thermal decomposition of the following high-purity salts of the five rare-earth elements--carbonates, chlorides, fluorides, nitrates, oxalates, and sulfates. X-ray diffraction patterns of the cubic and hexagonal oxides were indexed by a graphical method and patterns of the monoclinic oxides by Ito's method. The kinetics of crystallographic transformation were determined by high-temperature X-ray diffractometry. The kinetic data were interpreted using a shrinking sphere model. All of the transformations followed first order kinetics. Activation energies were calculated by application of the Arrhenius equation. These solid-state phase inversions were concluded to occur by a reconstructive transformation mechanism.

Jan 1, 1965

By L. H. Adami

The heats of formation of anhydrous cadmium sulfate, cobalt sulfate, copper sulfate, nickel sulfate, and zinc sulfate were determined by hydrochloric acid solution calorimetry. The values at 298.15° K for formation from the metal, rhombic sulfur, and oxygen gas follow (cal/mole): CdS04J -222.0 ± 0.3; CoS04, -212.0 ± 0.4; CuS04) -183.4 ± 0.6; NiS04, -208.1 ± 0.2; and ZnS04, -233.1 ± 0.2. Corresponding heats of decomposition to form the metal oxide, sulfur dioxide, and oxygen were derived from these results; heats of decomposition to form the metal oxide and sulfur trioxide were also derived.

Jan 1, 1965

By J. B. Gayle

The Bureau of Mines studied the effects of air oxidation on the recovery of float coal. Both batch-and continuous-type tests were made on six bituminous coals, representing the range in rank of coals now commercially used for carbonization, and on one anthracite coal. The effects on flotation recovery of oxidation at 1000 C for periods up to 50 days were investigated using an alcohol-type frother and a kerosine-pine oil reagent. Two series of release analysis tests were made, using one medium-volatile bituminous coal. Float coal recovery was adversely affected by oxidation in all tests where the alcohol-type frother was used. Conversely, a small degree of oxidation improved recovery with kerosine-pine oil frother for some of the coals in continuous tests. Prolonged oxidation (beyond about 14 days) adversely affected float coal recovery for all coals, the effect being more pronounced for batch-type tests and for tests using alcohol-type frother. Reagent selectivity for the rejection of both ash forming and sulfur bearing minerals was reduced by oxidation. Severe reduction of reagent selectivity required only about 3 days' oxidation for alcohol-type frother but more than 10 days' oxidation when the kerosene-pine oil reagent was used.

Jan 1, 1965

By T. E. Sterner

The Bureau of Mines investigated the use of a chromatographic gas analyzer in determining the concentration of combustion products in gas produced during field and laboratory thermal oil-recovery tests. Several parameters (carrier-gas flow, cell current, sample size, and temperature) known to affect quantitative analyses were studied using a commercially available dual-column, dual-detector chromatographic gas analyzer which had been modified to provide close control of these variables. The apparatus made possible a much closer control of air-and gas-injection rates and provided adequate data for performing material-balance calculations and for determining oxygen utilization during the laboratory and field combustion tests. The chromatographic analysis also aided materially in evaluating and measuring bypassing and gas travel times and in detecting high-permeability zones that were present in the reservoir.

Jan 1, 1965

By S. J. Aresco

The Bureau of Mines has been active in promoting the purchase of coal for Government use under specifications that define the requirements in terms of heating value of the coal, expressed in British thermal units, and the composition as shown by proximate analyses. To these, when required, are added the ash-softening temperature, the free-swelling index, and the Hardgrove grind-ability index. Under most of these specification contracts the bidders guarantee the quality of the coal, and that guaranteed by the successful bidder becomes the standard of his contract. The deliveries are sampled in accordance with instructions4 issued by the Bureau of Mines; the samples are analyzed in the Bureau laboratory to determine whether the coal is of the quality guaranteed by the contractor; if it is not, a price adjustment is made. Analyses of the delivered coal and tipple samples (samples collected at mine tipples as coal is being loaded into railroad cars or trucks) provide valuable data for use in evaluating future bids. In addition, the continuous sampling of coal as delivered is a check on the practical results obtained in burning the coal.

Jan 1, 1965

By M. R. Geer

Samples of coal from six beds in the Roslyn-Cle Elum field of Washington were subjected to float-and-sink tests to determine their amenability to the production of high-ash boiler fuel for on-site power generation. Grindability tests and analyses of ash were made. All of the coals would require some degree of cleaning to insure a product of 25 percent ash. With two of the coals the entire size range would have to be washed. With the other four, it would suffice to clean only the coarse coal and bypass the raw fines.

Jan 1, 1965

By R. E. Campbell

Uranium metal of improved purity was prepared by electrorefining commercial magnesium-reduced uranium in a molten sodium chloride-uranium trichloride electrolyte. The best operating conditions for the preparation of refined metal were established as follows: an electrolyte containing 8.7 to 13.3 weight-percent uranium; initial cathode current densities from 300 to 1,500 amp/sq ft; and a molten salt temperature of 860° C. Ingots produced from electrorefined uranium crystals prepared with these operating conditions were substantially free of metallic impurities. The only impurities in the refined and consolidated metal were present in low or undetectable amounts.

Jan 1, 1965

By B. W. Naugle

The Bureau of Mines investigated the changes that occur in decomposition products when coal is carbonized in a fluidized bed with steam as the fluidizing medium and the vapors are subsequently cracked without condensation in a fluidized bed of high-temperature coke. The coal used was from the High Splint bed, High Splint mine, Harlan County, Ky. Since this coal is agglomerating, it was blended with char. The integrated unit used in this investigation consisted of a 3-inch-diameter fluidized coal carbonizer, a 3.5-inch-diameter cracker containing a bed of high-temperature coke fluidized by the tar vapors and steam from the carbonizer, and gas-cleaning and product-recovery systems. The carbonizer was operated at 485° C and the cracker at 600°, 700°, and 800° C. The process variables investigated were temperature, residence time, and concentration (pound of tar vapors per pound of steam to the cracker) of tar vapors in the cracker. The total tar yields decreased as the temperature of the cracker increased, and at a constant cracker temperature of 600° C the yield of paraffins, acids, aromatics, and olefins in the distillate increased directly with the tar vapor concentration in the cracker. At 700° and 800° C only the acids and aromatics increased with increased concentration. Bases remained essentially constant regardless of the temperature and concentration. Similar results were obtained when the tar from the carbonizer was condensed prior to feeding to the cracker.

Jan 1, 1965

By Robert M. Becker

Particle mixtures were sampled in the laboratory, using ordinary sampling procedures, to determine whether or not the compound-multinomial probability distribution and other developments of part 2 agreed with experimental results. The objective was accomplished by the Bureau of Mines by comparing the moments and moment relationships of the appropriate probability models with their corresponding experimental values over a fairly wide range. The overall agreement between the corresponding theoretical and experimental values is both good and complete. The results demonstrate that sampling to a constant amount, such as weight, of items per sample is not the same, in general, as sampling to some constant number of items per sample. The results seem to confirm all the developments of part 2 and the application of the compound-multinomial function to bulk sampling.

Jan 1, 1965

By D. R. Mathews

The solubility of carbon in electrorefined vanadium was determined to be approximately 0.27 wt pct at the eutectic temperature 1,650° C and 0.03 wt pct at 700° C. The tensile strength and hardness of vanadium increased with car-bon content to the solubility limit, but this effect was small, probably because of the narrow solubility range. Between the solubility limit and 0.3 weight-percent carbon, the second phase had essentially no strengthening effect in vanadium. The second phase, observed metallographically at the grain boundaries and within the grains, was shown by autoradiography to contain high-carbon concentrations. This second phase was identified as VgC by X-ray analysis. The VgC in the grain boundaries contributed largely to the poor cold-and-hot workability of vanadium-carbon alloys. Increased concentrations of V2C occurred at the grain boundaries of the high-carbon alloy ingots as a result of homogenization at 1,600° C for 1 hour. Alloy ingots containing more than 0.36 wt pet carbon (a calculated 2.9 wt pct VaC) following homogenization, cracked severely and failed by intergranular fracture upon swaging at 900° C.

Jan 1, 1965

By Joseph Grumer

The range of composition of gases synthesized from solid fuels which are exchangeable with natural gas on current gas appliances was evaluated by theoretical principles. These principles consider primarily the flashback, blowoff, and yellow-tipping characteristics of air-entraining burner flames. It was found that complete identity between the synthetic and natural product is not necessary. Gases such as may be obtained by hydrogasification of coal and other solid fuels without the removal of unreacted hydrogen offer advantages in flame characteristics. Between 25 to 37 percent hydrogen can be tolerated in the sendout gas.

Jan 1, 1965

By G. A. Crowder

Far infrared spectra, most of them in the region 15-200 microns and for both the liquid or solution state and for the vapor state, were obtained for twenty-seven compounds.

Jan 1, 1965

By T. A. Sullivan

High-purity vanadium metal was prepared by electrorefining commercial vanadium in a molten sodium bromide, potassium bromide, and vanadium dibromide electrolyte. Variables investigated were operating temperature, current densities, electrolyte composition, and condition of the anode. The purity of the refined metal was in the range of 99.95 percent vana-dium. Iron and oxygen in the 50- to 250-ppm range were the only major impurities. Metal with hardness numbers of 50 to 60 in the Rockwell F scale was prepared from feed material with a Rockwell B hardness of 90. The arc-melted metal was highly ductile and could be cold-worked into sheet or foil.

Jan 1, 1965

By Jr. Gabler

Methods for the direct spectrochemical determination of impurities at the parts-per-million level in tungsten metal and oxide are presented. Several published procedures were investigated and numerous modifications were made in establishing procedures with improved precision and extended lower levels of determinability. Details of standards preparation are presented, experimental work is described, and three preferred methods are described in detail. A germanium carrier-distillation procedure is applicable to the determination of 13 elements in tungsten powder; a silver chloride carrier-distillation procedure provides for the determination of 24 elements in tungstic oxide, and a sustaining ac arc method is applicable to 26 elements in tungstic oxide. The choice of methods to be used depends upon sample form, elements and concentrations to be determined, and the precision and accuracy required. The investigations reported here were undertaken to develop direct spec-trochemical methods with increased accuracy and precision to determine impurities in high-purity tungsten and tungstic oxide, to define the lower concentration levels of detectability and measurement for the common impurities in tungsten by direct spectrographic means, and to present the details of the developed or modified methods that have proved applicable.

Jan 1, 1965

By T. C. Davis

Nine organic derivatives of fluorine, silicon, boron, and aluminum were purified for thermodynamic studies using distillation, zone melting, and gas liquid chromatography, The unusual properties of these compounds required the development of special techniques for handling and purification. To determine purities of purified samples, new techniques for analyzing spectral data were developed.

Jan 1, 1965