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By Heinz W. Sternberg

A method for the electrochemical reduction of the benzene ring was developed and applied to the electrochemical reduction of coal. Successive electrochemical reductions of a vitrain from low-volatile bituminous coal in ethylenediamine saturated with lithium chloride resulted in the addition of 53 hydrogens per 100 carbon atoms. Ultimate analyses and pyridine solubility of the vitrain recovered after each reduction showed that hydrogen added at the beginning has a much greater effect on solubility than hydrogen added at a later stage. Surprisingly, the removal of sulfur from the vitrain takes place only after the more reactive aromatic rings are reduced. Nuclear magnetic resonance analysis and average molecular weight determination of the extracts of the reduced vitrain samples, representing about 18 percent of the vitrain, showed that these fractions had 95 percent of their hydrogen content on saturated carbon atoms and an average molecular weight of 800 to 900. A study of the effect of operating variables on current efficiency showed that current efficiency is highest with aluminum as cathode material and with lithium chloride as electrolyte. A substantial increase in current efficiency of difficulty reducible olefinic double bonds was achieved by adding a proton donor. This result is significant in connection with the electrochemical reduction of coal which proceeds from readily reducible aromatic double bonds to difficultly reducible isolated double bonds. It is proposed that reduction is achieved by electrolytically generated and subsequently solvated electrons and hence does not require prior adsorption of the substrate at the electrode surface. This offers a distinct advantage for electrolytic reduction of sparingly or insoluble substrates such as coal.

Jan 1, 1967

By Robert E. Barieau

This report describes a method for treating pressure-volume-temperature (PVT) data obtained with a Burnett compressibility apparatus. The method makes use of a general nonlinear least-squares technique developed at the Bureau of Mines Helium Research Center. It is assumed that an adequate functional form is available for the expression of the compressibility factor as a function of either the molal density or the pressure. The functional form of the compressibility factor can be either linear or nonlinear in the parameters to be evaluated. Formulas are given for calculating variances and covariances of all parameters evaluated and for calculating the variance of calculated quantities of interest.

Jan 1, 1967

By L. C. George

The Bureau of Mines measured vapor pressures of selected mixtures in the binary system SnCla-ZnC12 by the static pressure method. Equations expressing the vapor pressure) and the heat and free energy of vaporization) as functions of temperature were developed by numerical analysis based on the sigma-plot method. It was found that the vapor pressure of any SnCl2-ZnCl2 mixture) at any temperature within the range of this investigation) could be accurately calculated from the derived values for the heat and free energy of vaporization for the mixture, with a probable error of 0.01 cm Hg or less.

Jan 1, 1967

By Manuel Gomez

Published experimental coke data from a pilot plant slot-type oven were examined by statistical regression analysis. Quantitative relationships were found to exist between the coking rate, bulk density, and fine grinding of the coal, sole-oven expansion, volatile matter, moisture, ash, and carbon con-tent of the coal and coke parameters indicative of size and strength. Regression equations developed from coke data were shown to yield computed values that were in good agreement with experimental results for 11 coke properties. Prediction equations developed were evaluated with an independent set of data. Present results indicate that the variables cited undergo much interaction and the sum of these interactions determines coke size and strength.

Jan 1, 1967

By Jr. Driscoll

The thermoelectric properties of yttrium monoarsenide, yttrium monoanti-monide) and ternary materials from the Y-As-Se and Y-Sb-Te systems were investigated by the Bureau of Mines from room temperature to 1,000° C. The maximum calculated figure of merit for yttrium monoarsenide and yttrium monoantimonide was 2 x 10-5 ° C-1. YAs and YSb were semimetallic conductors with low Seebeck coefficients and electrical resistivities. The values of the Seebeck coefficient and electrical resistivity of the Y-As-Se and Y-Sb-Te materials were between those of the yttrium selenides and tellurides and of YAs and YSb, respectively. The maximum power factor calculated for the Y-As-Se materials was 2 X 10-5 watt/cm ° C2 which yielded an estimated figure of merit of 6 X 10-4 0 C-1. Most of the Y-As-Se compounds had high Seebeck coefficients and moderately low electrical resistivities. The Y-Sb-Te materials were degenerate semiconductors with power factors of 6 X 10-8 watt/cm ° C2.

Jan 1, 1967

By Alla D. Mah

Heat content and entropy data at high temperatures were obtained for cuprous oxide (Cu2O) and cupric oxide (CuO). Experimental results and smooth values are reported. Equations are given for heat content increments and heat capacities above 2980 K. Low-temperature heat capacity data were obtained for cuprous oxide. Evaluation of the 2980 K entropy gave, S°298.15(Cu2O) = 22.08 ± 0.10 cal/deg mole. Heat of formation values were determined for cuprous and cupric oxides. The values are: AH°298.15(Cu2O) = -40,830 ± 300 cal/mole, and AH°298.15(CuO) = -37,230 ± 150 cal/mole.

Jan 1, 1967

By James H. Russell

The Bureau of Mines used a statistical approach to evaluate the effects of temperature, current density, and composition of the electrolyte on the purity of boron prepared by electrolysis of a fused mixture of boric oxide in potassium fluoborate. The quadratic equation which best fits the data was calculated for a temperature of 650° to 850° C, a cathode current density of 40 to 1,150 amp/ft2,and a boric oxide content of 0.3 to 7.1 molal. The best products, better than 95 percent boron, were obtained when the current density was less than 2 amp/ft2 and the boric oxide content was less than 2 molal.

Jan 1, 1967

By Hillary W. St. Clair

The effective coefficient for rate of reduction of a sample of granular iron ore may be determined by passing the reducing gas through a bed of the are at constant flow rate and periodically analyzing the effluent gas, The method of analyzing the data is based on a mathematical model that takes into account the variation in composition of the gas and solids with time and position in the bed. A method is described for determining the value of the rate coefficient that gives best agreement between the observed and calculated analyses of the effluent gas.

Jan 1, 1967

By Charles E. Whieldon

This report presents the results of a study on part of the Smithfield oilfield, Wetzel County, W. Va. The primary purpose of the investigation was to determine the original and the present volume of stock-tank oil in the formations and to investigate the feasibility of waterflooding the Gordon Stray, Gordon, and Fourth sands underlying the I. D. Morgan lease. The study was based on laboratory core analyses, geophysical well logs, geologic considerations, and various field prediction data from the I. D. Morgan lease. The Bureau found that, of the three sands cored, the Gordon Sand was the best prospect for waterflooding, and that a properly engineered water flood should recover 136 to 230 barrels of oil per acre-foot from this formation.

Jan 1, 1967

By James A. Wasson

This report analyzes the petroleum-production potential of the basal Greenbrier dolomite zone, Sycamore-Millstone field, Sherman District, Calhoun County, W. Va., through the application of certain secondary-recovery methods. The well logs obtained and the core recovered from a well in this formation permitted an evaluation of the productive capability of the reservoir, Approximately 120,000 stb of oil may be produced from a 20-acre five-spot unit at breakthrough if the property is waterflooded. At an assumed limiting producing gas-oil ratio of 20)000 sef/stb, approximately 69,000 stb of oil should be recovered by low-pressure gas drive.

Jan 1, 1967

By Paul Sands

Single- and two-stage tests were made with 6-inch, coal-cleaning hydrocyclones to determine the effect of hydrocyclone geometry, operating conditions, and feed composition on performance. Most of the testing was conducted in an open-circuit pilot plant that had a maximum capacity of about 9 tons per hour. The coals used in the investigation had top sizes of 1/4 inch and 28 mesh. Considerable latitude was found in the range of geometry variables that could be used without affecting performance adversely, although a certain minimum ratio of overflow to underflow openings had to be maintained for best operation. Two-stage cleaning proved distinctly better than operation with a single hydrocyclone, because clean coal lost in the refuse product of the primary unit can be partly recovered in the secondary. There is an unusually great difference in the specific gravities at which the individual sizes of the feed are separated in the hydrocyclone. This militates against high efficiency because maximum yield occurs when all sizes are cleaned at the same specific gravity. The size composition of the feed and, more particularly, the size composition of the impurity have a greater influence on the efficiency attainable in the hydrocyclone than in most other types of fine-coal cleaners.

Jan 1, 1968

By R. S. Fowkes

Jetstream pressure distributions and coal cutting rates were determined for a number of nozzles and under different operating conditions. The jetstrearn pressure distribution data were fitted to an assumed curvilinear equation by the utilization of a numerical least-squares technique with the aid of a digital computer. Subsequent manipulation of the approximation equation showed that the total force of the jetstream, rather than its maximum pressure or total kinetic energy per unit Lime, was the most significant quantity affecting the coal cutting rate. A shorter method for assessing the ability of a nozzle to cut coal was found.

Jan 1, 1968

By R. J. Leary

This investigation was conducted to determine the effects of various rare-earth metal addition practices upon the macrostructure and the pattern of sulfur distribution in steel ingots. Heats of plain carbon steel were melted in a 1-ton, basic electric-arc furnace. Melts were treated with mixtures of rare-earth silicides, aluminum, and cryolite either in the furnace before tap or in the ladle after tap to determine the effects of this form of rare-earth treatment upon ingot macrostructure. Steels thus treated with rare earths in the furnace were characteristically free of the gross subsurface nonmetallics which typically result from conventional rare-earth treatments. Steel treated in the ladle showed only a few such nonmetallics, and practical techniques were developed for eliminating most of these. Results showed that furnace deoxidation was controlled by the concentration ratio of rare earths: aluminum. During casting, deoxidation was controlled by the concentration of rare earths. Oxygen contents equivalent to vacuum ladle degassing resulted from air-melt furnace treatments with the rare-earth mixtures described. Rare earths in steel inhibited the onset of equiaxed grain formation during ingot freezing, and also virtually prevented interdendritic segregation of sulfides.

Jan 1, 1968

By M. R. Geer

The Bureau of Mines examined the washability data for 25 Appalachian coals requiring low-density washing to reduce sulfur content to 1 percent, using the distribution-curve method. The purpose was to estimate how closely theoretical sulfur values could be approached, what yields of washed coal could be expected, and the recovery efficiencies that might be achieved. Assuming that the run-of-mine coal would be crushed to 3/8 inch and cleaned in dense-medium cyclones, the calculations indicate that theoretical sulfur contents could be approached closely when cleaning at a specific gravity of separation as low as 1.30. With coals that have favorable specific gravity compositions the recovery efficiency anticipated for cleaning at 1.30 specific gravity is surprisingly high. Similar calculations for cleaning with concentrating tables at intermediate specific gravities indicated that theoretical sulfur contents at 1.50 specific gravity could be approached closely with some coals but not with others. The calculations suggest that operating a table at a specific gravity of separation much lower than about 1.50 probably would be unsatisfactory with most coals.

Jan 1, 1968

By Philip C. Tully

These modifications to the Redlich-Kwong equations for pure hydrogen and neon were developed after an unsuccessful attempt to generalize a modification technique previously developed for helium. New coefficients of the B terms were developed by minimizing the residuals. No changes were made in the coefficients of the A terms. For normal hydrogen, B was changed to [0.08063Tc PcT] for temperatures from 980 to 423° K and pressures up to 1,050 atm. The average deviation in Z was 0.36 percent with maximum deviations less than 1 percent for all but a few low-temperature points. For neon, B was changed to [PCT 0.1025T], for temperatures from 120° to 973° K and pressures up to 1,500 atm. The average deviation in Z was 0.34 percent with maximum deviations less than 1 percent for all but a few high-pressure and low-temperature points. Efforts to attain a lower temperature range to comparable accuracy with this type of modification were unsuccessful. In the range of applicability, these equations should be used with caution when calculating derived thermodynamic functions, such as the isobaric specific heat.

Jan 1, 1968

By D. J. Bauer

A primary amine extraction system was investigated for fractionating a cerium-group, lanthanide sulfate mixture. Addition of diethylenetriaminepenta-acetic acid (DTPA) to the amine extraction system resulted in separation factors as high as 5.4 for lanthanum-cerium, 8.0 for cerium-praseodymium, 3.7 for praseodymium-neodymium, and 7.0 for neodymium-samarium. In multistage studies on a cerium-free lanthanide mixture, 96 percent of the lanthanum was recovered with a purity of 95 percent.

Jan 1, 1968

By Kenneth J. Miller

To determine the effectiveness of the many new flocculants available to the coal industry 20 of these reagents were evaluated treating slurry feeds to four refuse thickeners. Settling rates and supernatant liquid clarities were determined for each of the flocculants on the four slurries, and zeta potential measurements of the slurry solids were made. The test results showed that the flocculants provided comparable results when judged categorically as anionic, nonionic, or cattonic. It was also apparent that control of zeta potential insures maximum benefit from a flocculant.

Jan 1, 1968

By John M. Gomes

A two-phase molten halide-silicate technique for extracting tungstic oxide (WO3) from scheelite (CaW04) and wolframite [(Fe, Mn)W04] was investigated. The halide phase extracted over 99 percent of the was, whereas the lower silicate phase retained about 90 percent of the calcium, iron, or manganese oxides. The most efficient extraction and separation of tungsten from scheelite was accomplished at 1,080° C in a molten system containing, in mole-percent, 9 calcium tungstate (CaW04), 42 sodium chloride (NaCl), 28 sodium fluoride (NaF), 17 sodium metasilicate (Na2SiO3), and 4 alumina (Al2O3). Wolframite was also treated at 1,0800°C; the molten system contained, in mole-percent, 11 (Fe, Mn)W04, 74 NaCl, and 15 Na2 SiO3.

Jan 1, 1968

By M. R. Geer

The ever-increasing need to guard against stream pollution has intensified interest in the problems of handling and disposing of flotation tailing. Therefore, the Bureau of Mines investigated the possibility of using crushed washery refuse to adsorb the free water in thickened flotation tailings on a bench scale and then in a pilot plant because the conventional methods of disposing of coal flotation tailings--impounding them or filtering them so they are dry enough to be conveyed to the refuse dump--are sometimes either impractical because of space limitations or costly because of low filter capacity. Most of the refuse samples tested were of similar mineralogical composition and exhibited similar water retention capability. The amount of crushed refuse required to adsorb the water in a particular tailing was influenced greatly by the fineness of the solids in the tailing and hence the percentage of solids to which it could be thickened. The ratio of crushed refuse to tailing solids required to provide a mixture dry enough to be carried on an inclined conveyor belt varied from 2.4 to 6.4. Several chemical agents that were tested were very effective in turning the free water in tailings into a stable gel. Fly ash also was very effective in adsorbing water.

Jan 1, 1968

By B. D. Nash

The object of this research was to investigate the technical feasibility of preparing chromium metal by the thermal decomposition of bisbenzene chromium. Bisbenzene chromium, a pi-bonded sandwich type organometallic compound, was thermally decomposed under reduced pressure to form a metal plate on a heated substrate. Metal recovery was close to 100 percent of theoretical, with deposition rates up to 20.8 mg/hr/cm2. Metal purity was dependent not only upon the purity of the starting material, but also upon the sublimation rate of bisbenzene chromium. Total detectable metallic impurities ranged from a low of 18 ppm to several hundred ppm. In general, metallic impurities were less than 100 ppm. Carbon, the major nonmetallic impurity, ranged from less than 0.3 percent to more than 10 percent. The carbon contamination is most likely a result of the decomposition of the organic portion of bisbenzene chromium. An unusual property of some of the deposits was their outstanding corrosion resistance. Unlike pure electrolytic chromium, which dissolves readily, these deposits were insoluble in hot mineral acids.

Jan 1, 1968