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By Charles Prasky

The objective of this investigation by the Bureau of Mines was to determine the response to sulfatization of diverse low-grade manganiferous materials in the iron formation of the Cuyuna district. In line with this objective a bench-scale sulfatizing procedure was developed that was less expensive and more rapid than pilot-plant methods. Samples from the central and south- western parts of the North range were tested. Results of evaluating a total of 46 pelletized samples, originating in areas with an estimated potential resource of 94 million long tons with a manganese content of 7 percent, indicates that approximately 87 percent of the manganese may be recovered as a synthetic manganese ore. This is equivalent to more than 12 million long tons of a metallurgical-grade ore, containing 46 percent manganese. It is anticipated that a premium product, containing over 50 percent manganese, may be obtained by sulfatizing procedures. This report is part of a continuing investigation5 6 of Cuyuna iron range manganese deposits in Crow Wing County, Minn. Lewis and coworkers describe the manganiferous iron formation in the bedrock of the Cuyuna district and include a description of a high-temperature differential sulfatizing process for recovering a ferrograde manganese product. The low-grade manganiferous

Jan 1, 1961

By Harry R. Nicholls

A simple economical method has been developed for determining the in situ longitudinal and shear velocities in rock from which its elastic constants can be calculated. By detonating small charges of high explosives in shallow drill holes near a free surface, both longitudinal and shear waves were generated simultaneously. Accelerometers and velocity gages mounted to the rock surface were used to record the arrival time for both waves over travel path lengths from 50 to 450 feet, Measurements were made in two rock types. From the arrival time measurements, the longitudinal and shear wave velocities were calculated. From these velocities and the density of the rock, the elastic constants were calculated. The dynamic elastic constants of drill core samples of the two rock types were determined in the laboratory by the resonant-frequency method, The lab- oratory and in situ elastic constants are compared and significant differences noted. In general, there is less spread in the in situ data than in the laboratory data, and Poisson's ratio does not fall outside the theoretical limits for the in situ data as is often the case for laboratory-determined elastic constants.

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

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 L. M. Burman

The phase-boundary pressure required to maintain a natural hydrocarbon fluid in a single phase must be considered in planning the recovery of reservoir liquids by miscible-phase processes. The change in the phase-boundary pressure at reservoir temperature that results when a light component or a mixture of light components is added to a reservoir fluid is an especially important consideration. The cricondenbar pressure (maximum phase-boundary pressure) and the critical pressure are unique correlated pressures that have been utilized to calculate the change in phase-boundary pressure that may result when the composition of a reservoir liquid is altered by an additive. In this study one reservoir oil and three gas-condensate fluids are used as examples. Correlations pertaining to the critical and cricondenbar states in chapters 4 and 5 of Bureau of Mines Monograph 10 (3)5 were used to demonstrate how butane and lighter components added to these reservoir fluids affect their phase-boundary pressures.

Jan 1, 1962

By R. V. Higgins

Many contributions to methods of forecasting the performance of waterfloods of a five-spot pattern have been made by investigators. In most of these forecasting methods, a previously selected sweep efficiency is used, and other simplifying assumptions are employed to obtain the objective. In this paper the calculated oil recoveries from several five-spot single- and multiple-layer stratified reservoirs were made with a minimum of assumptions, and because of the techniques used, no previously selected sweep efficiency was required. As a result, the accuracy of the forecast is increased. Permeability curves and continuously changing saturation gradients are used in every section of the pattern. By means of a potentiometric model, the flood pattern is divided into channels, the centers of which are the streamlines. The channels are divided into cells. As flood water enters, the permeability and saturation of each cell change with time. In this study the production from multiple-sand layers of different absolute permeability but with the same relative permeability-saturation relations are combined. The results are shown for a single- and 10-layer reservoir with a permeability variation of 0.60. The oil rate, water-oil ratio, and recovery are shown as functions of time for a 2- and 20-centipoise oil starting in primary phase and after fill-up.

Jan 1, 1962

By Wesley Holmes

Concentrating, nodulizing, and smelting studies were conducted at the Albany Metallurgy Research Center of the Bureau of Mines to determine whether (1) western iron ores of the type found in the Carter Greek deposit near Dillon, Mont., could be utilized; (2) concentrates of acceptable grade with good iron recovery could be attained by wet-magnetic beneficiation; (3) nodulized concentrates could be smelted with reductants readily available in Montana; (4) iron concentrates could be smelted without prior agglomeration; and (5) high-purity iron could be produced directly from high-grade concentrates, Three small samples and two tonnage samples from the Carter Creek deposit were uniform in chemical composition, and their iron content averaged about 31 percent. They were found to be banded gneisses, and magnetite was the principal iron-bearing mineral.

Jan 1, 1962

By A. C. Rice

Investigation of a variety of mines to determine efficiency for rare- earth extraction has resulted in a solvent extraction technique wherein Primene 81-R,4 N-benzylheptadeeylamine (BHDA), and Primene JM-T give favorable extraction from sulfate solutions. Extraction from chloride, nitrate, and perchlorate solutions is negligible. Distribution coefficients for 10 rare-earth elements with Primene 81-R establish an extraction sequence beginning with lanthanum and proceeding through lutetium according to atomic number. Yttrium and ytterbium are exceptions in the extract ion sequence.

Jan 1, 1962

By A. F. Colombo

Laboratory-scale tests were conducted by the Bureau of Mines on an argillaceous Michigan copper ore and mill tailing to determine the feasibility of leaching with acidified ferric sulfate solutions. The ore and tailings, containing 1.24 and 0.24 percent copper, respectively, were from the White Pine Copper Co., Ontonagon County, Mich. The investigation showed that ferric sulfate leaching of the ore and tailings followed a predictable pattern. Thus, with 4 hours of leaching, up to 58 percent of the copper in the ore was extracted, but prolonged leaching (2 to 3 weeks) was required to dissolve more than 90 percent of the copper. Similarly, about 50 percent of the copper in the mill tailings sample was dissolved in a few hours, but 8 days or more were required for extractions of over 90 percent.

Jan 1, 1962

By G. W. Birge

Carbonizing properties of the principal coal beds of Perry County, Ky., are described in this Bureau of Mines report. Seven samples, representing the Hindman, Flag, Haddix, and Fire Clay beds, were carbonized by the Bureau of Mines-American Gas Association (BM-AGA) method, and yields of products and physical properties of cokes were determined. Carbonizing properties of blends of Flag and Fire Clay coals, with 20 and 30 percent Pocahontas No. 3 low-volatile coal from McDowell County, W. Va., also were determined. Expanding properties of the Flag and Fire Clay coals and their blends were determined in the Bureau of Mines sole-heated oven. The Perry County coals tested are high-volatile A bituminous in rank and, with the exception of the Hindman-bed sample, which contained excessive sulfur, were chemically suitable for metallurgical use. The three coals tested in the sole-heated oven contracted less than normal for Appalachian coals of similar rank, Blending the Fire Clay and Flag coals with 20 or 30 percent low-volatile coal increased coke strength appreciably but increased the expansion beyond normal limits for industrial blends.

Jan 1, 1962

By G. W. Birge

Carbonizing properties of the principal coal beds of Butler County, Pa., are described in this report by the Bureau of Mines. Eight samples, representing the Upper Freeport, Lower Freeport, Upper Kittanning, Middle Kittanning, Lower Kittanning, Clarion, and Brookville beds, were carbonized at 900° C. by the Bureau of Mines-American Gas Association (BM-AGA) method. Butler County coals rank as high-volatile A bituminous and are generally characterized by high sulfur content compared with Appalachian coals used for industrial coking. If cleaned, the Brookville and one sample of Upper Freeport coal would be acceptable as the major component of metallurgical coking blends. The other Butler County coals tested would be unsuitable for this purpose because of either excessive sulfur or poor coking properties.

Jan 1, 1962

By A. A. Berk

The Bureau of Mines devised a test nipple for the field study of corrosion in the condensate-return lines of Federal heating plants. Corrosion surveys, made with this device, showed that the deterioration of the piping was caused principally by carbonic acid in the steam condensate. Corrosion problems were brought under control when the carbonic acid concentration in the condensate was decreased. In many instances, this was effected by decreasing the total carbon dioxide content of the feedwater; in others, the condensate acidity was neutralized with volatile, alkaline chemicals. Filming treatment with octadecylamine, reported successful in controlling return-line corrosion in industry, was much less effective in Federal area-heating plants. Laboratory study by the Bureau disclosed that octadecylamine is unstable in heating systems. Analytical methods were developed for this chemical and its degradation products in heating-plant condensate. Field surveys, in using these methods, confirmed the instability of the filming material. Laboratory tests showed that the degradation products are not useful film formers. Since filming treatment has little effect on condensate corrosivity, the piping was corroded where it was not coated by the treatment chemical.

Jan 1, 1962

By D. W. Scott

Thermodynamics is a powerful tool for investigating rotational isomerism in substituted ethanes and related molecules. Accurate calorimetric data can be interpreted to give information, not only about the energy difference between conformations, but also about the shape of the potential barrier hindering rotation from one conformation to another. However, a deterrent to this use of thermodynamics is the labor required to calculate the contributions to the thermodynamic functions for assumed potential functions. Tables of thermo-dynamic contributions for appropriate potential functions can eliminate that labor and greatly facilitate the thermodynamic study of rotational isomerism. In this research, tables of contributions to the thermodynamic functions were compiled for two potential functions typical of some commonly encountered examples of rotational isomerism. TYPES OF POTENTIAL FUNCTIONS Potential function 1, illustrated in figure 1, A, has two equal minima higher than the third. It has the general shape of the barrier to internal rotation in n-butane, for example. The trans conformation of n-butane has the lowest energy, and the two skew or gauche conformations have equal but higher energy. Potential function2, illustrated in figure 1, B, has two equal minima lower than the third. It has the general shape of the barrier in 2-methylbutane, for example. The two C1 conformations of 2-methylbutane have equal energy much lower than the assumed Cs conformation, which has not been observed spectroscopically.

Jan 1, 1962

By W. H. Ode

An investigation of standard methods for determining ash in low-rank* coals showed that generally 60 to 95 percent of the total sulfur in the coal is retained in the ash as SO3. This large sulfur retention causes a positive error in the determined mount of ash of as much as 6 percentage points for the coals examined, although it usually is 2 to 3 percentage points for lignites and about 1 for subbituminous coals. Unless the sulfur content is low or unless a correction is made for the SO3 retained, the fixed carbon and oxygen have an equivalent negative error when determined by difference; also other inaccurate analytical values occur when the data are calculated on an ash- free bas is. No simple modification of the ashing procedure was found that would reduce the sulfur retention to a point where its effect on the ash determination would not be significant, Therefore, for accurate analytical work on law-rank coals, the SO3 should be deducted from the determined ash to obtain a "corrected" ash value.

Jan 1, 1962

By John Ward Smith

The potential economic value of oil shale depends on the products from thermal degradation of the rock, because no other practical method for producing valuable material from oil shale has been found. Detailed study of thermal degradation behavior can aid in characterizing oil shales and their deposits and in evaluating oil-shale processing methods, Numerous publications describe various pyrolysis properties of oil shales (see surveys 3, 9, 11 and articles 1, 2, 4-8, 10, 12),4 but they do not describe a generally applicable analytical procedure for detailed evaluation of thermal degradation products. The analytical method presented here for such evaluations is designed to provide for: 1. Control of retorting conditions--temperature, heating, rate, reaction atmosphere--plus some control over retort pressure and carrier-gas flow, 2. Precise direct gravimetric measurement of the thermal degradation products--oil, water, gas, and spent charge (residue after thermal treatment of the charge). 3. Samples of all products. 4. Determination of the identities and amounts of gaseous compounds produced. 5. Elemental analysis and gross heating value of all products. 6. Determination of the distribution in the retorting products of the elements present in the original samples.

Jan 1, 1962

By Gerald W. Elger

This report compares the quality of zirconium metal prepared by batch reduction of zirconium tetrachloride by (1) sodium, (2) magnesium, and (3) mixtures of sodium and magnesium. Criteria for quality are based on chemical analyses and hardness testing of zirconium arc-melted from sponge. The best quality zirconium with respect to low oxygen content and hardness numbers was prepared by reaction of zirconium tetrachloride with a mixture of sodium and magnesium. It was found that this reaction could be successfully carried out by two methods: (1) addition of sodium and magnesium before the initial reaction and (2) periodic injection of sodium during reaction of zirconium tetrachloride with magnesium. The largest quantity of metal was found to be recovered from experiments in which a mixture of sodium and magnesium was used. Magnesium appeared to be a better reductant than sodium because magnesium-reduced zirconium contained less oxygen and exhibited lower hardness numbers than sodium-reduced metal.

Jan 1, 1962

By T. T. Campbell

This investigation was undertaken by the Bureau of Mines to determine if high-purity ductile molybdenum of uniform quality can be prepared by bomb reduction techniques. Molybdenum trioxide (Mo03) and mixtures of molybdenum dioxide (Mo02) and trioxide were reduced by magnesium in closed steel bomb reactors. Very high pressures in excess of 5,000 p.s.i. developed during magnesium reductions of Mo03. The addition of calcium oxide to the bomb charges caused a significant reduction in pressure. Reaction efficiencies higher than 95 percent were obtained during magnesium reductions of either Mo03 or mixtures of Mo02 and Mo03, but high pressures were encountered when the charges contained from 30 to 60 percent Mo02. Reaction efficiencies were usually low (less than 80 percent) when the bomb charges contained more than 40 percent Mo02. The charges with the best composition considering operating pressure, yield, and purity contained from 10 to 30 percent Mo02. The addition of small amounts of carbon to the reaction charges was helpful because some deoxidation occurred during the reduction and also during subsequent arc-melting of the regulus metal. The purity of the bomb-reduced, arc-cast molybdenum metal ranged from 99.2 to 99.8 percent and in some instances the metal contained as little as 5 parts per million oxygen.

Jan 1, 1962

By C. J. Chindgren

Upgrading of commercial red cake and recovery of vanadium oxide from uranium-vanadium mill solutions were investigated by the Bureau of Mines. Alternative procedures potentially useful for manufacture of high-quality vanadium oxide at the mill site were explored and developed. The simplest and best procedure for converting commercial red cake containing about 10 percent combined sodium and potassium oxides (Na20) (K20) into a 98- to 99-percent vanadium pentoxide (V205 product appeared to be a metathesis in an ammoniacal solution of ammonium sulfate. Molybdenum, as well as the alkali metal oxides, was removed from the red cake by this procedure at a modest expenditure of labor and reagents. When preparing vanadium oxide of higher grade, it was necessary to dissolve the red cake and reprecipitate the vanadium as ammonium metavanadate. Calcination at 450° C, decomposed the metavanadate and yielded oxide of about 99.5 percent V205. By recyrstallizing the metavanadate before decomposition, an oxide product approaching 99.9-percent purity was obtained.

Jan 1, 1962

By E. L. Singleton

This Bureau of Mines investigation was initiated to study and establish some of the chemical and physical characteristics of the condensed Mno-Si02 system. To prevent oxidation of the manganous ion, I atmosphere of purified helium was used in the furnaces. Solidus-liquidus curves and invariant points were established from melting-point determinations and were supplemented from data obtained by the static-quenching method. Experimental findings and data are for the intermediate compounds of tephroite and rhodonite with their respective eutectics represented at 25.5 and 37.2 weight-percent silica. Tephroite melts congruently at 1,347° C., and rhodonite melts incongruently at 1,286° 8.. A metastable transformation was determined to exist at the 1,347° C. isotherm, the congruent melting point of tephroite. A composite X-ray-diffraction pattern was formulated for synthetic rhodonite. This investigation contributes fundamental data leading toward a better understanding of the more complex slag systems.

Jan 1, 1962

By V. E. Edlund

Pyrometallurgical studies by the Bureau of Mines demonstrated the feasibllity of sintering and smelting a low-grade flotation concentrate made by pilot-plant processing 10-percent manganese ore from the Maggie Canyon deposit, Mohave County, Ariz. Under optimum conditions 85 percent of the manganese in a flotation concentrate that assayed 36 percent manganese was recovered as standard ferromanganese. A blend of this flotation concentrate with high-grade dithionate pilot plant precipitate was similarly processed with a recovery of 90 percent of the manganese. Thorough mixing and pelletizing of the charge before treatment on the sinter hearth was necessary to produce a well agglomerated product by single pass sintering. Although satisfactory sinter was produced from a variety of material combinations, best results were obtained on a charge that contained 80 percent flotation concentrate and 20 percent return sinter fines. This combination was mixed with 6 percent coke, based on weight of concentrate; and 12 percent moisture. Sintering such a charge yielded a well agglomerated product containing over 80 percent coarse material, The results of standard crushing tests showed that the product was physically comparable to iron ore sinters and manganese nodules.

Jan 1, 1962