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By Carl Rampacek

The conversion of dilute sulfur dioxide gas into sulfuric acid by autoxidation in mechanical cells of the flotation or gas absorber types was investigated. Bench-scale tests were made with sulfur dioxide-air mixtures to determine the influence of several factors on autoxidation of sulfur dioxide, using iron and manganese salts as catalysts. The laboratory investigation subsequently was extended to pilot plant acid-making tests, using a modified turbomixer gas absorber having a 12-inch-diameter impeller. Sulfur dioxide gas was produced for the tests by roasting pyrite in a fluidized-bed reactor. In the better tests, made with manganese sulfate as the catalyst, the equivalent of 1,000 pounds of anhydrous H2SO4 was produced per 24 hours as a 10-percent solution; power consumption was 0.2 kwhr per pound of equivalent anhydrous acid synthesized. The batch and continuous tests demonstrated the technical feasibility of producing dilute sulfuric acid by autoxidation of sulfur dioxide gas in mechanical cells when converting pyrite roaster or waste smelter gases.

Jan 1, 1963

By H. C. Carpenter

Lignite tar made by low-temperature Lurgi-Spülgas carbonization of North Dakota lignite was hydrocracked in single-pass, fixed-bed operation at 3,000 pounds per square inch over cobalt molybdate catalyst to produce gasoline, and at the same pressure, over zinc chromite catalyst to crack the high-boiling phenolic compounds to low-boiling phenolics. Hydrocracking the raw tar or the creosote-oil fraction from the tar over cobalt molybdate removed most of the oxygen, sulfur, and nitrogen in the forms of water, hydrogen sulfide, and ammonia, and produced gasoline yields from 31 to 59 volume-percent. The gasoline fractions contained from 0.1 to 7.7 volume-percent tar acids, but tar-base percentages were too low for reliable measurement; removal of these materials with dilute caustic and acid solutions also reduced the sulfur and nitrogen to 0.01 weight-percent or less.

Jan 1, 1963

By Robert S. Warfield

The Bureau of Mines investigated a geologically favorable area in the Beluga River coalfield in south-central Alaska to determine if there were sufficient minable coal reserves for onsite utilization to meet the projected thermal power needs of the Anchorage area. A program of diamond core drilling and sampling delimited a shallow saucerlike structure estimated to contain indicated reserves of more than 20 million tons of subbitminous coal in a seam over 50 feet thick that could be mined by opencut methods. A large sample of fresh coal was taken across the full width of the seam for washability studies. This sample, with 4 volume-percent of clay partings eliminated, contained 24.4 percent moisture and 16.8 percent ash and had a calorific value of 7,162 Btu per pound. The studies indicated that mechanical cleaning would be of doubtful value.

Jan 1, 1963

By A. R. Taylor

The Bureau of Mines has determined the heat capacity and enthalpy values for beryllium sulfate (BeS04) throughout the temperature ranges of 10° to 300° K in an adiabatic calorimeter, and 350° to 860° K in a Bunsen-type ice calorimter, The heat-capacity data were extrapolated to 0° K, and smooth values of heat capacity, entropy, enthalpy function, and free-energy function were reported at 10-degree intervals between 0° and 300° K. The method of least squares was used to fit the enthalpy data with an algebraic equation. The equation also was used to calculate values of heat capacity, entropy, enthalpy function, and free-energy function at 50-degree intervals between 300° and 900° K.

Jan 1, 1963

By L. J. E. Hofer

This Bureau of Mines study, part of a broad program of research in air pollution related to minerals, was conducted to determine the nature and extent of the poisoning of catalysts when used to remove certain air pollutants from exhaust gases. The poisoning examined in this investigation occurs when leaded gasoline is used as a fuel for automotive engines. This research was conducted in cooperation with the Public Health Service. The smog in the Los Angeles area is attributed to the effect of radiant energy on the mixture of hydrocarbons and nitrogen oxides found in the atmosphere there. A large portion of the hydrocarbons is believed to originate in the exhaust gases of automobiles. To prevent the escape of these hydrocarbons into the atmosphere catalytic mufflers have been proposed. In principle, these are simple and nonmechanical, consisting of a vessel charged with a catalyst capable of destroying the exhaust hydrocarbons by catalyzing their oxidation. However, these catalysts are severely affected by the particulate matter, mainly in the form of lead sulfate (PbS04), lead oxysulfate (PbS04.Pb0), and Lead chlorobromide (Pb(Cl,Br)2), contained in the exhaust gas. Deposition of lead on the catalyst as PbS04, PbS04, PbS0, and Pb(Cl,Br)2 restricts catalytic activity. As a result,after 20,000 miles of operation the temperature necessary to achieve 50-percent conversion of isopentane in a mixture of 0.2 percent isopentane, 2 percent carbon monoxide and 4 percent oxygen, and the balance nitrogen at 10,000 hourly space velocity has risen from 400° C. to 500° C. even with a catalyst taken from the exit portion of the catalyst bed. The rest of the catalyst was more severely affected. Therefore, it would appear that operation for 20,000 miles is near the limit for a catalyst.

Jan 1, 1963

By G. W. Birge

Twenty-eight samples, representing the Pittsburgh, Lower Kittanning, Stockton-Lewiston, Coalburg, Winifrede, Cedar Grove, Peerless, No. 2 Gas, Powellton, and Eagle 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. Expanding characteristics of 22 of the samples were determined in the Bureau of Mines sole-heated oven. The Kanawha County coals tested were high-volatile A bituminous in rank, with dry, mineral-matter- free fixed- carbon contents ranging from 53.9 to 66.3 percent. With few exceptions, they were chemically satisfactory for metallurgical use, and most of the coke-strength indexes were within the industrially accepted range for high-volatile blending coals.

Jan 1, 1963

By W. W. Weller

Low-temperature heat capacities of scandium sesquioxide (Sc203) and a mixture of cerium sesquioxide (Ce203) and cerium dioxide (CeO2) were measured over the temperature range from 50° to 298° K. The entropy of scandium sesquioxide at 298.15° K was evaluated directly as S°298.15 = 18.4 ± 0.1 cal/deg mole. That of cerium sesquioxide was extracted by combining the heat-capacity data for the mixture with those for pure cerium dioxide; the result was S298.15 36.0 ± 1.0 cal/deg mole.

Jan 1, 1963

By Walter C. Lorenz

Samples of materials containing pyrite from various coal mines and coalbeds were studied to compare their compositions and oxidizing characteristics. Pyrite was the only form of iron sulfide identified, but X-ray diffraction, emission spectrography, and microscopic analyses revealed similar suites of minerals and trace elements. The pyrite occurred usually in spherical clusters of very small crystals. The oxidation of pyrite in solutions of PeSO4 and Fe2(SO4)3 and in the presence of an iron oxidizing bacterium Ferrobacillus ferrooxidans, was studied through a manometric technique. FeS04 or Fe2(SO4)3 solutions had no appreciable influence on pyrite oxidation under the test conditions, The bacterium acted as a catalyst, greatly increasing the oxidation rates; however, in three samples that also contained calcites, bacterial oxidation was greatly reduced. The oxidation rates also increased approximately as the percentage of pyrite in the samples increased. For the series of samples studied, there was no definite correlation of the results with the location of the various mines nor with the acidity of alkalinity of the mine drainage.

Jan 1, 1963

By C. L. Chaney

Investigations were conducted to develop spectrochemical methods capable of determining 0.01 to 100 micrograms of metals in 50 milliliters of solution. The use of gallium hydroxide (Ga(OH)3) as a carrier-precipitant to concentrate metallic ions is described. A porous-cup graphite electrode is used to collect the precipitate. A specially designed plunger permits the electrode assembly to serve as the sample-containing electrode in the subsequent spec-trographic analysis. Analytical curves are presented for antimony, arsenic, beryllium, and zinc. Sensitivities of detection are given for 13 elements. The techniques were applied to identify impurities separated from tungsten, to determine trace impurities in solutions containing high concentrations of magnesium, cobalt, or nickel, and to identify trace impurities in hydrofluoric acid. Laboratory glassware was a serious source of contamination when low levels of zinc were determined.

Jan 1, 1963

By R. Barany

The heats of formation of gehlenite and talc were determined by hydro-fluoric acid solution calorimetry. The results are reported in terms of the constituent oxides (?H298.15 = -31.1 ± 0.5 kcal/mole for gehlenite and ?H298.15 = -44.9 ± 0.3 kcal/mole for talc) and in terms of the constituent elements (?H298.15 = -952.8 ± 0.7 kcal/mole for gehlenite and ?H298.15 -1,415.5 ± 1.4 kcal/mole for talc).

Jan 1, 1963

By P. G. Clites

This study was undertaken to determine the effect of consumable-electrode vacuum arc melting on the properties of copper and to determine the applicability of the process to the production of cast shapes of copper. Ingots and castings were produced from electrolytic tough pitch copper (ASTM designation ETP), from electrolytic cathode copper (ASTM designation CATH), and from oxygen-free copper (ASTM designation OF). The products of this study were evaluated to determine the effect of the melting process on the removal of impurities from the copper and on the physical properties of the copper. The results indicate that consumable-electrode arc melting can be satisfactorily applied to the melting and casting of copper. Ingots prepared directly from electrolytic cathode copper contained slightly higher levels of impurities than are found in commercial oxygen-free copper, Excellent results were obtained with centrifugal castings of unalloyed copper, and reasonably successful static castings can be produced if proper mold and gating systems are employed.

Jan 1, 1963

By W. T. Abel

Laboratory tests were conducted with a closed, recycling system to evaluate the effectiveness of solid-in-gas suspensions as heat transport mediums. Micronized graphite in helium or nitrogen was circulated by a centrifugal compressor to determine the feasibility of the method and heat transfer capabilities of the mediums. Suspensions were circulated without plugging or eroding the compressor or piping. At low flowrates and light (0.1 to 0.2 volume-percent) graphite loadings, slightly less power was required to transport a given amount of heat with suspensions than with helium alone. Graphite deposition on the heat exchange surfaces of the cooler decreased the heat transfer effectiveness at higher solids concentration. Efforts to eliminate deposition are described.

Jan 1, 1963

By A. A. Cochran

The objective of the research was to determine the final distribution of cerium additions to steel, their effect on sulfide inclusions, and the usefulness of radiotracer methods in investigating steel problems. Fifty-gram heats of steel were prepared that contained either cerium 141 and nonradioactive sulfur, or sulfur 35 and nonradioactive cerium. These steels were studied by autoradiography, measurements of their surface radioactivities, optical microscopy, and chemical analysis. Samples of the crucibles were analyzed quantitatively for cerium or sulfur by radioactivity counting methods. The addition of cerium to steel melts reduced the size and number of iron sulfide inclusions in the resulting steel. A significant fraction of the sulfur and most of the cerium penetrated into the MgO crucible during the melting operation, The cerium inclusions in steel were identified as cerium sulfide. Radiotracer methods were found to be versatile and highly sensitive.

Jan 1, 1963

By M. J. Kovalik

The effect of oxidation by air at temperatures ranging from 200° to 390° C on the change of chemical and physical properties of Pittsburgh-bed coal was studied as a function of processing time and temperature. The goal was to prepare a nonagglomerating fuel from a strongly coking coal for use in continuous carbonizing processes and in fixed-bed gasifiers. The oxidized coal was carbonized in a bench-scale apparatus, and the coke strength was evaluated in a Roga tumbler. Strength of the coke was progressively reduced with time of oxidation until the coking power of the coal was apparently destroyed. Time requirements to obtain an essentially nonagglomerating product were inversely related to processing temperature. Gaseous products released from the coal during oxidation reduced the yield of the desired nonagglomerating product, which decreased with time of oxidation at constant temperature and with increase in processing temperature at equal time. Oxidation at a temperature slightly above the lower limit of the plastic temperature range of Pittsburgh-bed coal was most effective because of the short processing time required and moderate processing losses.

Jan 1, 1963

By R. E. Mussier

This investigation was made to study new methods to prepare high-purity yttrium metal, Various methods were used to prepare pure intermediate compounds, primarily chlorides, bromides, and iodides, which were subsequently reduced to metal. The process found most suitable for the preparation of pure anhydrous yttrium chloride involved thermal dehydration of a mixture of hydrated yttrium chloride and ammonium chloride while under vacuum. Yttrium bromide and iodide were prepared most effectively by the direct halogenation of yttrim carbide. Yttrim carbide was obtained by reacting and melting yttrium oxide-carbon mixtures in a carbon-arc furnace. Yttrium halides were purified by vacuum distillation and reduced by alkali or alkaline-earth metals. Lithium and sodium proved to be the best reductants from the standpoint of yield (>95 pct) and purity (>99.8 pct) of the yttrium. The product of the reduction step was sponge metal, which was consolidated readily by conventional cold-mold, arc-melting procedure. The purest yttrium obtained in laboratory scale work was prepared by sodium reduction of yttrium chloride and contained only 125 pp oxygen; other impurities did not exceed 1,000 ppm. In larger scale tests yttrium containing only 800 to 1,000 ppm total impurities was obtained by lithium reduction of yttrium chloride. The tensile properties of high-purity yttrium were determined. Mechanical tests showed that yttrium can be forged, extruded, rolled, spot welded, and deep drawn.

Jan 1, 1963

By L. H. Adami

This paper reports the results of solution calorimetry conducted to obtain the heats of formation of crystalline FeS04?6.952H20 and FeS04?1.008H20, from. which values were derived for the stoichiometric compounds FeS04?H20 and FeS04?H20. Also included are derived values of the free energies of formation and dehydration. This work was undertaken primarily to fill a need for data for pure, easily obtainable ferrous compounds that are suitable for use as calorimetric intermediates, The ferrous sulfate hydrates meet the essential requirements for this use.

Jan 1, 1963

By G. W. Birge

Carbonizing properties of the principal coalbeds of Elk, Clarion, Jefferson, Clearfield, and Centre Counties, Pa,, are described in this Bureau of Mines report, Twenty-six samples, representing the Upper Freeport, Lower Freeport, Upper Kittanning, Middle Kittanning, Lower Kittanning, and Brookville beds, were carbonized by the Bureau of Mines--American Gas Association (BM-AM) method, and yields of products and physical properties of cokes were determined. Expansion or contraction of the majority of the samples was measured in the Bureau of Mines sole-heated oven. Chemical analyses, agglutinating values, and free-swelling indexes are given for all samples. In this area the coals generally are characterized by high sulfur and moderately high ash content, and their suitability for metallurgical use would depend largely upon satisfactory cleaning. The samples from Elk, Clarion, and Jefferson Counties were high-volatile A bituminous In rank, whereas, most samples from Clearfield County and all those from Centre County were of medium-volatile rank. Coals from Clarion County had dry, mineral- matter-free fixed-carbon contents ranging from 56.5 to 60.3 percent and were weakly coking. With the exception of two samples which contained excessive ash, the medium-volatile coals of Clearfield and Centre Counties were strongly coking and, as indicated by sole-oven expansion results, would require blending with lower rank coal to avoid oven damage.

Jan 1, 1963

By J. G. Donaldson

A bench-scale method for recovering lead and zinc from slimes and mill tailings from the Tri-State District of Missouri, Oklahoma, and Kansas was developed by the Bureau of Mines. Dilute hydrochloric acid, containing sodium chloride, and chlorine gas were used to decompose the mineral constituents. Lead was electrolyzed from the pregnant acid solution, and zinc was precipitated from the depleted electrolyte by neutralization with lime. Up to 98 percent of the lead was recovered in an impure lead electro- deposit assaying approximately 85 percent lead. Zinc recoveries up to 90 percent of the total were attained in a precipitate assaying approximately 40 percent zinc.

Jan 1, 1963

By C. O. Hawk

As an exploratory effort to produce useful products from coal by a new path, the Bureau has made a few experiments on the fast heating of finely ground coal particles by irradiation with a flash of high intensity light. The flash was produced by an electrical discharge at high voltage through a xenon-filled tube. The flashes lasted from 2 to 3 milliseconds. The reaction took place in small sample tubes, ½ inch-dimeter by 4 inches long, and with small amounts of coal (total amount charged 0.1 gram, probable effective amount not more than 20 milligrams). Average particle size of the coal, estimated on a numerical basis, was 20 microns. Temperatures reached were evidently quite high, because all products obtained in quantity were characteristic of high temperature pyrolysis. Apparently, conversion of the coal was extensive where isolated particles received the full benefit of a flash. It seems particularly significant that acetylene was present in appreciable amounts--comprising almost 3 percent of the total gaseous product in one case. This is good evidence of a short heating period to very high temperature (well above 1,000° C) followed by rapid quenching. Although the results are interesting, they do not suggest any immediate practical application.

Jan 1, 1963

By C. M. McKinney

This report contains Bureau of Mines analyses of 291 samples of crude petroleum from the Gulf Coast Area of Louisiana and Texas. Included are 65 analyses from 51 Louisiana fields and 226 analyses from 216 Texas fields. Analyses from the Texas fields include 90 from 58 Upper Gulf Coast fields, 47 from 28 Middle Gulf Coast fields, and 89 from 40 Lower Gulf Coast fields. The analyses represent fields that produced 1,000 barrels or more per day during at least one of the years 19.57 through 1961, with the exception of 23 analyses from the Texas fields. The fields considered are listed by state and geographical groupings, with field names arranged alphabetically within each grouping. The tabulation also includes information concerning the geological sources of the samples. General characteristics of the crude oils and analytical and computed data determined from the analyses are summarized. Crude oil production data are given for the fields for 1960 and 1961 and are cumulative through 1961.

Jan 1, 1963