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By Paul S. Lewis

The Bureau of Mines hydrogenated coals of different rank that had been irradiated with either x-rays or gamma rays. Lignite, high-volatile A and C bituminous, and low-volatile bituminous coals were exposed to l billion roent¬gens of gamma-ray radiation; specimens of high-volatile A and C bituminous coals from other sources received 6 million roentgens of X-ray radiation. Irradiated and unirradiated control specimens of those coals were hydrogenated in autoclave experiments at (6,000-p.s.i. final pressure and 400° C. with retention times of 15, 30, or 60 minutes depending on the coal rank and catalytic treatment. Comparison of results from irradiated specimens with those from the control experiments showed that the radiation had no beneficial effect on the coal. High-volatile C bituminous coal may have been affected by radiation more than the other coals. One billion roentgens appeared to reduce the amount of coal converted to liquids and gases by about 10 pct., and 6 million roentgens reduced it by about 6 pct. then catalyzed with tin. In all other cases, the conversion of irradiated coal was either reduced by as much as 4 pct. or was essentially the sank as that obtained with unirradiated coal. Irradiation during hydrogenation nay be effective for increasing the reactivity of coal and should be investigated; further work with coals irradiated prier to hydrogenation is not recommended.

Jan 1, 1962

By G. E. Johnson

A bench-scale study was made of removing hydrogen sulfide from synthesis gas at elevated pressure by iron oxide impregnated on wood chips. The gas contained 0.02 to 0.06 percent oxygen. The removal of hydrogen sulfide by iron oxide impregnated on wood chips is more efficient at elevated pressure. At constant space velocity, longer periods of operation at 400 p.s.i.g. are possible before the exit gas reaches a given maximum concentration of hydrogen sulfide, compared with 200 p.s.i.g. or atmospheric pressure. In tests at room temperature, 60° C., and 100° C., the most effective removal of hydrogen sulfide was obtained at room temperature and the least effective at 100° C. Dry impregnated wood chips removed only about half as much hydrogen sulfide as chips wetted to a water content of 50 percent.

Jan 1, 1962

By A. D. Hahn

This report describes reconnaissance by the Bureau of Mines of titanium-bearing beach sands on Ship Island in the Gulf of Mexico off the south coast of Harrison County, Miss. The purpose was to determine the ilmenite, rutile, and associated heavy-mineral content of black-sand-bearing beach sands. The investigation was part of a survey of titanium resources of the United States. Ilmenite (FeTi03), an iron-titanium oxide, is the major titanium-bearing mineral consumed in the titanium pigment industry. Rutile (TiO2), titanium dioxide, is used mainly as a constituent in welding-rod coatings and in producing titanium metal. The major fieldwork was conducted during the first half of February 1961. Nine holes, totaling 220 feet of bore, from which 110 samples Her taken, were drilled at widely spaced intervals on the island.

Jan 1, 1962

By M. E. Tyrrell

Lightweight basic refractories suitable for use in some sections of the all-basic furnace were developed. Potential advantages of such refractories are lower weight, improved resistance to thermal shock, and less tendency to spall off the working face. Plant trials in positions not subject to heavy loading or severe erosion seem warranted. Forsterite (2MgO.SiO2), stabilized dolomite (2Ca0?SiO2 + MgO), and chrome-spinel [(Fe,Mg)0?(Cr,Al) 031 refractories were fabricated using bubbles as the principal component in the brick mixtures. Bubbles were blown from melts of the basic raw materials as they were tapped from a conducting-hearth arc-resistance furnace. The bubbles were graded, bonded with synthetic Forsterite plus mineralizers, dry-pressed, and fired to temperatures of 1,600° C. or over in a gas-fired kiln. Refractory properties of the bubble brick were compared with those of insulating refractories made by burning combustibles out or dense brick mixtures. Lightweight refractories fabricated of bubbles were one-third lighter in weight than dense bricks of like materials. Their mechanical strength was satisfactory, and their resistance to thermal shock was excellent. In tolerance to open-hearth slag and in resistance to thermal shock, the chrome-spinel bubble bricks wore the best of the refractories tested. Basic refractories of the insulating type were about 40 percent lighter in weight than dense commercial refractories, but they were mechanically weak and not suitable for superduty service.

Jan 1, 1962

By Alfred V. C. Meyer

A Blastcorder4 was calibrated on the Bureau of Mines shaking table in the frequency range of 12 to 40 c.p.s. and in the amplitude range' of 0.25 to 1.0 g. The results of this calibration study show that in the frequency range of 12 to 30 c.p.s. the average accuracy of the Blastcorder is approximately ± 0.1 g.

Jan 1, 1962

By Raymond W. Hiteshue

Experiments were conducted al temperatures of 480° to 800° C. and hydrogen pressure of 6,000 p.s.i.g. to determine the effect of coal residence time on the conversion of a high-volatile bituminous C coal to liquid and gaseous products when using a semicontinuous apparatus designed fur rapid heating and cooling of reactants. The objective of the studies at high temperatures was to determine if appreciable quantities of coal could be converted to gaseous hydrocarbons and low-boiling liquid hydrocarbons. Experiments at lower temperatures were designed to indicate shifts in product distribution with respect to temperature and to learn more about the general mechanism of the reaction when using close control of coal residence time. One percent molybdenum, based on m.a.f. (moisture-and ash-free) coal, was used throughout this investigation. At 800° C., 6,000 p.s.i.g., and "zero" residence time) the yield of gaseous hydrocarbons was about 38 percent and the yield of oil about 4.5 percent, based on m.a.f. coal. With IS minutes residence time, under the same conditions, the yield of gaseous hydrocarbons was approximately 80 percent with no increase in yield of oil. Apparently at 800° C., and hydrogen pressure of 6,000 p.s.i.g. coal was rapidly carbonized to char with expulsion of volatiles. Char was then slowly hydrogenated to gaseous hydrocarbons without production of oil.

Jan 1, 1962

By J. R. Welty

High-temperature thermodynamic data have, in recent years, become increasingly important for the extractive metallurgist. The extraction of metals from their ores previously was based on trial and error methods, involving hours of testing and often costly equipment fabrication. Using thermodynamic data it is frequently possible to predict the feasibility of a proposed metallurgical process as well as the optimum operating conditions for the process with reasonable accuracy. Such predictions can save consider-able tim~ and expense. Widespread use of thermodynamic analyses has been handicapped by lack of dependable experimental data. Investigators, notably K. K. Kelley (4)4. have devoted many years to determining and compiling such data. These investigators, although prolific in their production of thermodynamic values, have been unable to meet all the needs of industry and other branches of science. This becomes obvious when one considers the aeronautical and nuclear fields, in which previously unimportant, therefore uninvestigated, substances have become of prime importance.

Jan 1, 1962

By Louis P. Domingues

As part of a study on high-temperature ceramic materials, the ammonium sulfate, carbonate, nitrate, oxalate, and sulfate salts of yttrium, lanthanum, and cerium were analyzed thermogravimetrically. The temperature ranged from room temperature to 1,500° C. Each salt was decomposed by heating at a rate of 2.5° C. per minute, and some of the salts were subjected to additional rates of 5° C. per minute or 10° C. per minute. The decomposition sequences have been identified, and the temperatures of formation of intermediate compounds and of the oxides have been determined. The minimum oxide formation temperature of a given lanthanum salt exceeds that for the similar salt of yttrium, and both exceed that for the same salt of cerium except for one cerium carbonate. Variation of the heating rate indicates a thermal lag in the materials and produces the shift of formation temperatures to higher values and loss of resolution in the weight-loss distribution as the heating rate increases.

Jan 1, 1962

By P. G. Barnard

The Nation's steel industry is largely dependent on shipments of manganese from foreign sources for steel production. An adequate substitute for the manganese requirements of our present steel technology would improve our national self-sufficiency and also contribute substantially to the conservation of our manganese resources. As each of these objectives is a major interest of the Bureau of Mines, possible substitutes for manganese in steel were investigated. Titanium was selected as the most promising substitute because the published results of several investigations indicate that titanium would perform the most obvious function of the manganese in steel: The elimination of iron sulfide and its deleterious effects. The investigation involved extending the published data on titanium additions in steel to provide enough information for an accurate evaluation of the practical value of the substitute. Therefore, quantitative data were obtained on the partition of sulfur and carbon between iron and relatively small titanium additions.

Jan 1, 1962

By Henry E. Blake

The purpose of this Bureau of Mines investigation was twofold. The first phase of the work was to determine the technical and mechanical feasibility of defluorinating low-grade siliceous fluorspars on an intermediate scale by high-temperature pyrohydrolysis in a rotary kiln. The second phase was to react the liberated hydrogen fluoride (HF) offgas with alumina monohydrate to produce commercial-grade aluminum fluoride (85 percent AIF3). The two phases of the work were to be integrated into a single continuous process. Evaluation of the data shows that low-grade siliceous fluorspars can be successfully defluorinated, either in a solid or a molten state, in a gas-fired rotary kiln in the presence of water vapor at 1,250° to 1,350° C. The water produced by combustion of propane was sufficient to yield defluorinatians of 75 to 85 percent.

Jan 1, 1962

By Robert K. Koch

Laboratory-scale studies on defluorination of natural and synthetic fluorspars by pyrohydrolysis at 1,500° C. were made to determine the feasibility of developing a process for producing hydrogen fluoride from siliceous fluorspars. It was found that the reaction (at 1,500° C.) is not promising for process development, even though a silica-free offgas can be generated. The primary difficulty is the low hydrogen fluoride content of the offgases; an HF content of 6 percent was the best achieved. Previous research by the Bureau of Mines has demonstrated that offgases averaging 27 percent hydrogen fluoride can be produced under carefully controlled conditions at 1,280° C. The lower temperature process is a better method for production of HF. However, charges in which the CaF to Si02 mole ratio varied from 0.4 to 2 could be processed with similar results. Also, combined alumina and ferric oxide contents up to 25 mole-percent did not noticeably alter the rate of defluorination. Therefore, virtually any natural siliceous fluorspar would respond in essentially the same manner when exposed to water vapor at 1,500° C.

Jan 1, 1962

By L. B. Pankratz

Present-day interest in the rare-earth elements and their compounds, for both metallurgical and ceramic uses, makes it highly desirable to accumulate basic thermodynamic data that can be applied to theoretical considerations of the processing of these substances. Such data still are seriously lacking. This Bureau of Mines paper reports the results of high-temperature heat content measurements of the sesquioxides of four rare-earth elements--europium, gadolinium, neodymium, and samarium--and of the closely related element, yttrium. The temperature ranges covered by the measurements are as follows: Monoclinic Eu2O3, 298°-1,802° K. Cubic Eu203, 298°-1,350° K. Monoclinic Gd203, 298-1,802° K. Cubic Gd203, 298°-1,550° K. Hexagonal Nd203, 298°-1,795° K. Monoclinic Sm203 298°-1,798° K. Cubic Sm203, 298°-1,149° K. Cubic Y203, 298°-1,799° K.

Jan 1, 1962

By Alla D. Mah

The need for more and better basic thermodynamic data for the oxides of many of the rare metals is evident to anyone who attempts thermodynamic calculations involving these substances. In continuation of a Bureau of Mines program to meet this need, this paper reports new experimental values of the heats of formation at 298.15° K. of the hexagonal crystalline variety of germanium dioxide and germanium dioxide glass. The values were obtained by means of combustion calorimetry and sodium hydroxide-solution calorimetry. The calorimetric results also made possible the derivation of values for the heat and entropy of fusion of hexagonal germanium dioxide at its melting point. The newly measured data were combined with previously known entropy and high-temperature heat content values to obtain heats and free energies of formation of germanium dioxide (in the hexagonal crystalline, glassy, and liquid states) over the temperature range from 298.15° to 2,000° K.

Jan 1, 1962

By Robert F. Stewart

The oxidation of structural materials at high temperatures in gas-cooled systems can be greatly retarded by the addition of small amounts of hydrogen to the inert coolant. In experimental equipment for gasifying coal with heat transferred by helium, the oxidation of graphite and metals (molybdenum, tungsten, and certain stainless steels) by trace impurities in the coolant helium was virtually eliminated by adding 0.1 to 1.0 percent hydrogen. The reaction of hydrogen with praphite does not preclude its use to retard oxidation; at 2,400° F. only 0.2 pound of graphite per square foot per year is lost for each percent of hydrogen in the helium. The addition of hydrogen appeared to prevent the mass transfer of carbon often associated with oxidation of graphite, without causing noticeable embrittlement of stainless steels and molybdenum or other damaging effects. This method has been tested in precision gas-recycle systems and applied successfully for more than a year in a pilot-scale unit operating at 250 pounds per square inch gage and 2,400° F. It is now used routinely and can be applied to many gas-cooled systems operating at high temperatures.

Jan 1, 1962

By F. H. Gibson

In recent years physico-chemical techniques have been applied for rapid analysis of coal and coke ash as replacements for classical wet-chemical methods. Although the classical methods are accurate, they are time consuming because many chemical separations are necessary to complete an analysis, and they require skilled analysts for accurate work (12).4 For the past several years the Bureau of Mines has applied some of the newer physico-chemical techniques in its continued search for new and improved methods at analysis. The methods of analyzing coal and coke ash evolved from this work include spectrophotometric methods far SiO2, A120, , Fe203 , TiO2, and P2O5; chelatometric titration for CaO and MgO; and flame photometry for Na20 and K2O. The methods are rapid and direct, are suitable for analyzing a group of samples at the same time in production work, and dire results with almost the same accuracy as classical procedures. With the new methods, complete analyses in duplicate can be obtained at a rate of 2 to 3 times that of conventional methods.

Jan 1, 1962

By Joan T. May

Anhydrous methods were tested for the extraction of beryllium from low-grade source materials. The purpose of the investigations was to find new extraction processes that are applicable to domestic ores. Beryl, helvite, and phenacite materials containing from 0.1 to 2.8 percent BeO were used as starting materials for direct halogenation tests and pretreatment followed by halogenation. The results of the investigations showed that direct fluorination and carbide-chlorination are two practicable methods that can be applied to low-grade concentrates. Treatment of concentrate-carbon mixtures with anhydrous hydrogen fluoride extracted 99 percent of the beryllium in the concentrate; the soluble fluoride product, converted to an oxide, contained 70 percent BeO. Chlorination of beryllium-silicon carbide, prepared from low-grade concentrates, extracted beryllium into the volatile chloride product.

Jan 1, 1962

By Martin H. Stanczyk

Two methods of recovering zinc from zinc ammonia complex solutions were investigated. One method studied was distillation of the ammonia from the solutions to recover a basic zinc sulfate, which after calcining to zinc oxide was reduced to metallic zinc using hydrogen at 900° C. The second method tested was electrolysis. The tests were made of synthetic and leach solutions analyzing about 80, 100, and 115 gpl (grams per liter) of Zn, NH3, and SO4, respectively. The leach solutions were prepared by oxidation leaching of a sphalerite flotation concentrate, assaying 55 pct zinc at elevated temperature and pressure. The distillation method recovered about 98 pct of the zinc in a product analyzing 97 pct zinc. Ammonia losses incurred during the leaching and distillation operations were about 0.1 lb per lb (pound per pound) of metallic zinc produced. Electrolysis of the solutions at a cathode current density of 25 amp per sq ft (ampere per square foot) yielded zinc deposits assaying in excess of 99.9 pct zinc. About 1.5 kwhr (kilowatt-hour) of power were consumed per pound of zinc deposited; the current efficiency was 72 pct. Other electrodeposition tests revealed that small amounts of ferric iron in the cell liquor were deleterious to electrolysis unless about 5 lb of glue per ton of zinc were present in the electrolyte. The use of glue and vigorous agitation of the electrolyte gave smooth zinc deposits from solutions containing as much as 0.1 gpl iron.

Jan 1, 1962

By C. W. Dwiggins

This report describes the development, theory, and application of techniques and instruments for quantitatively determining nickel, vanadium, and iron in oils, using direct, X-ray emission spectrographic methods (5, 6).3 The methods developed apply to petroleum and other oils as well as some specific fractions of oils. The quantities of nickel, vanadium, and iron in various petroleums are of practical and theoretical interest. Even traces of nickel and vanadium may poison cracking catalysts, and X-ray methods have been used for determining nickel in such catalysts (7). At least parts of the nickel and vanadium occur as metal-porphyrin complexes, a fact which may have considerable bearing on knowledge of the origin of petroleum.

Jan 1, 1962

By E. G. King

As low-temperature heat-capacity and entropy data were available for only one sesquisulfide (cerium sesquisulfide), it appeared desirable to augment the information for this class of compounds by measuring the sulfides of antimony and indium. In addition a pressing need existed for data on indium sulfide to supplement vaporization studies in progress in the Department of Mineral Technology, University of California. This Bureau of Mines paper reports low-temperature heat-capacity measurements and entropy evaluations at 298.15° R. of antimony sesquisulfide of stoiehiometric composition (Sb2S3) and of indium sesquisulfide which was somewhat deficient in sulfur (In2S2.93). The data for the latter substance were adjusted to correspond to the stoichiome tric composition (In2S3 ) . Indium sesquisulfide has a lower entropy at 298.15' K, than either antimony sesquisulfide or cerium sesquisulfide, in line with the higher atomic density of the indium compound.

Jan 1, 1962

By Harry R. Nicholls

The objectives of this investigation were to determine the strain propagation laws for a strain pulse in salt and to compare the seismic effects from the detonation of different explosives in salt. The investigation showed that a strain propagation law of the type, e = K(R/W 1/3 ) n, and a strain energy propagation law of the type, Ea/W 1/3 = K(R/WI/3)b , are valid in salt. A change in the regression law coefficient, n , was noted with strain level. A similar change in b was inferred because strain energy is proportional to the square of strain amplitude. Particle velocity data may be used interchangeably with strain data under the test conditions.

Jan 1, 1962