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By David J. Kusler

This report describes a primary or direct, continuously sampling, and automatically averaging gravimetric method for analyzing gaseous mixtures of carbon dioxide, carbon monoxide) hydrogen, and (by volume measurement) nitrogen. The gaseous mixture is analyzed by passing it at a controlled and definite rate through a system that permits carbon dioxide and water retained by appropriate absorbents to be determined and the residual-gas volume (essentially nitrogen) to be measured. The accuracy and dependability have been established by comparison with very carefully conducted Orsat analyses. The method was developed for, and has been satisfactorily applied to, the analysis of blast-furnace top gas. It permits relatively attention free operation, using simple and low-cost materials usually found as basic equipment in the analytical laboratory. It provides, over a wide range of time or sampling intervals (from less than 1 to over 24 hours), the average composition, in terms of volume-percent, for those components usually determined in blast-furnace gas, if (as is usual) the flow rate of gas from the blast furnace is essentially constant over a selected analysis interval. Oxygen and methane are not determined; but, since these gases are normally absent or present only in traces, their analysis is seldom required.

Jan 1, 1959

By B. C. Parks

This paper is a report on the relationships between petrographic composition, chemical composition, physical properties, and thermal behavior of banded bituminous coal. It describes the relationships between petrographic composition, behavior in various laboratory tests, and carbonizing properties of different petrographic types of coal that occur in relatively thick benches in a single bed of high-volatile A bituminous coal - the Hernshaw bed of Boone County, W. Va. Thin-section microscopic analysis and free-swelling index determinations of the thin-section samples were made of a standard column sample. A standard face sample, a representative channel sample, and representative samples of two prominent petrographic benches of bright and dull coal were subjected to chemical analyses and free-swelling-index, plasticity, dilation, agglutinating, low-temperature carbonization, and BM-AGA retort tests. A float-and-sink separation was also made of part of the standard face sample. The fractions from this gravity separation were subjected to petrographic and chemical analysis and free-swelling-index, plasticity, and dilatation tests.

Jan 1, 1959

By L. Allan White

Instrumental analysis is an indispensable tool to many phases of research on rare-earth metals and their compounds; therefore, the development of new and improved instrumental techniques is essential. This report describes an emission spectrometric analytical method using direct-current carbon-arc excitation of various rare-earth-oxide mixtures. Lanthanum oxide serves the dual purpose of an internal standard and a constant major constituent. The versatility of the method was demonstrated by three different applications: (a) Analysis of complex rare-earth concentrates; (b) determination of impurities in high-purity rare-earth oxides; and (c) detection of rare-earth elements in other types of matrices, such as those resulting from beneficiation of rare-earth ores. The average error of analysis in the concentration range of 0.2 to 10.0 percent was 14.6 percent for a group of complex synthetic mixtures of rare-earth oxides. An average error of analysis in the concentration range of 0.05 to 0.50 percent was 21 percent for a group of high-purity rare-earth oxides.

Jan 1, 1959

By D. E. Wolfson

This report describes the carbonizing properties of the principal coal beds of Allegheny County, Pa., which rank low in the high-volatile A bituminous classification. Seven coal samples from 3 coal beds were selected for study, as follows: 2 each from the Redstone and Pittsburgh beds and 3 from the Upper Freeport bed. Selection was based on estimated reserves. The samples of Upper Freeport and Pittsburgh coals were satisfactory chemically for producing metallurgical coke. The ash contents of the samples of Redstone coal were moderately high. One of the samples of Redstone coal was high in sulfur content, and it would be difficult to upgrade to meet present metallurgical standards.

Jan 1, 1959

By J. J. Demeter

As part of its work on converting coal to fluid fuels, the Federal Bureau of Mines has been studying the synthesis of liquid fuels from carbon monoxide and hydrogen by Fischer-Tropsch synthesis. A fluidized bed of nitrided, fused-iron catalyst has been operated successfully to produce high yields of oxygenated compounds. Trouble-free operation continued for over 800 hours, and the test was terminated voluntarily. About 85 percent of the fresh feed was converted when the unit was operated at a space velocity of 500 hr.-1, a 12:1 recycle-to-fresh-feed-gas ratio, a 300-p. s. i. g. pressure, and a temperature of 252° C. When operating at a fresh-feed-gas space velocity of 1,000 hr.-l and a 9:1 ratio of recycle to fresh gas, conversion of fresh feed was 68 percent, and the product yield was 235.9 grams per cubic meter of synthesis gas converted. The oxygenate and C5 and heavier hydrocarbon yield was 110.6 grams per cubic meter of gas converted, 83 percent of this was oxygenates. The atom ratio of N:Fe of the catalyst, initially 0.455, decreased to 0.288 by the end of the 800-hour experiment. Nevertheless, the yield of oxygenated compounds per cubic meter of H2 + CO converted at the end of the run was approximately the same as that obtained 500 hours earlier with identical operating conditions. X-ray analysis of the discharged catalyst indicated that only ?-iron carbonitride was present. Sieve analysis of the discharged catalyst indicated that only 2 percent of fines was produced during the reduction, nitriding, and synthesis.

Jan 1, 1959

By Arnold B. Hubbard

This report presents a hydrogenolysis study undertaken to obtain information on the constitution of the kerogen or organic material in Colorado oil shale and to determine some of the properties of the hydrogenolysis products. The high yield of hydrogenolysis products was separated, so far as possible, into type compounds; a number were identified. The results thus obtained were used as a basis for proposing the possible existence of certain structures in kerogen. To the authors' knowledge, few or no hydrogenolysis studies have been made of Colorado oil-shale kerogen by others. However, this method has been used in studying the constitution of coal. In general, the coal studies involved treating pulverized coal at different temperatures and hydrogen pressures with different catalysts. In some instances different solvents were used during the treatments.

Jan 1, 1959

By Kenneth Lipman

Auxiliary equipment was assembled around a purchased oscillograph to permit observation of the current and voltage characteristics of low-energy, capacitance-discharge sparks having durations of at least 10 mµ-sec. Circuit details of the assembled apparatus, performance characteristics of the complete system, and some preliminary data from representative self-initiated sparks are given in this report. INTRODUCTION One of the subjects of continuing research by the Federal Bureau of Mines Division of Explosives Technology is the ignition of explosive-gas mixtures by means of low-energy capacitance sparks. Quite early in these investigations it was recognized that understanding the gas-ignition phenomena would be facilitated by detailed information about the performance of the ignition source (spark) under the actual conditions of interest; however, the sparks of practical interest are nonrepetitive transient phenomena whose duration could reasonably be estimated to be in the time range of 1 mµsec. to 1 µsec. As such, the only feasible method of obtaining detailed information was and is oscillographic representation of the pertinent current and voltage transients. It was not until 1947 that a suitable, commercial, dual-channel oscillograph could be obtained as the basic instrument for these studies; the instrument specified in 1947 was delivered in 1950. This paper describes the auxiliary

Jan 1, 1959

By E. L. Litchfield

Spark ignition of combustible-gas mixtures is a relatively old subject of investigation and has been treated both experimentally and analytically by many people. Elements of static and current electricity are almost always present in mining and industrial operations, and the spark can be an extremely efficient source of ignition. Thus the practical interest of such problems as the "intrinsic safety" of electrical apparatus is obvious. Ignition and quenching phenomena are the primary laboratory representatives of combustion phenomena that are dynamically nonsteady, and such nonsteady phenomena playa considerable part both in industrial processes and in safety matters, although they are of less immediate practical interest. Considerable effort has been expended by the Federal Bureau of Mines in investigations of spark ignition.5 6 7 8/ Primarily, this work has established the significance of several of the parameters involved. Although the

Jan 1, 1959

By W. W. Agey

Under terms of cooperative agreements, the Federal Bureau of Mines Inter-mountain Experiment Station assisted the General Services Administration (GSA) in operating the manganese-ore purchasing depots at Deming. N. Mex., and Wenden, Ariz. A resident metallurgist stationed at the depots directed sampling of the ore lots for assaying, took samples for amenability testing, calculated acceptances for payments to shippers, and served as technical adviser to the depot manager. The Intermountain Experiment Station at Salt Lake City, Utah, tested the amenability of the ores to determine how much of the manganese could be recovered in concentrates assaying a minimum of 40 percent manganese (Mn) and containing a maximum of 16 percent iron (Fe), 15 percent silica (Si02) plus alumina (AI203), 0.3 percent phosphorus (P), and I percent copper (Cu) plus lead (Pb) plus zinc (Zn). All chemical analyses of the ores and test products were done at Salt Lake City. In all, 567 ore lots submitted to the Deming depot were tested by flotation to determine their amenability to concentration into specification-grade material; 421 lots were amenable, and 146 were unamenable, primarily because of high copper content or excessive silica or iron in the flotation concentrate. Chemical analyses totaling 42,700 were made on the ores submitted to the Deming depot and on the products of the amenability-test program.

Jan 1, 1959

By J. B. Gayle

The Bureau of Mines sole-heated oven has been used for studying coal expansion for some 20 years. During the period before 1940 emphasis was placed on studies of the mechanism of coal expansion and the effects of variations in operating conditions on the results. Since 1940 emphasis has shifted to a survey of the expansion properties of various coking coals. Because additional information concerning a number of unsolved problems in connection with the earlier studies appeared highly desirable, this investigation of the use of sole-heated ovens for studying coal expansion was undertaken. The principal findings, in order of their discussion in the text, may be summarized as follows. 1. Expansion results for binary blends of coking coals exhibit nonadditive behavior, both positive and negative deviations from additive behavior being noted, depending on the particular coals tested. Additive behavior can be achieved, however, either by charging the blend components in separate layers (which indicates that the observed phenomena are not characteristic of the particular expansion oven used) or by testing relatively coarse sizes of coal (which suggests that the effects of crushing on the expansion properties of coking coals may be even more complex than is generally recognized).

Jan 1, 1959

By W. M. Mahan

This report describes work carried out by the Federal Bureau of Mines in cooperation with the General Services Administration (GSA). Tests on nickel oxide reduction were conducted at the Pyrometallurgical Laboratory at Pitts-burgh and Bruceton, Pa., and at a rented plant at Canonsburg, Pa. Nickel oxide was reduced to sponge nickel, which was then melted to produce specification-grade nickel ingots containing a minimum of 98.50 percent nickel plus cobalt and a maximum of 1.00 percent cobalt. One purpose of this study was to determine if specification-grade nickel could be made from nickel oxide produced at the United States-Government-owned plant at Nicaro, Cuba, in pilot-plant scale operations involving direct reduction and melting processes. A second and equally important purpose was to obtain cost data on the pilot-plant operation to estimate the cost of producing ingot nickel at an annual rate of 12 million pounds. Laboratory tests verified that nickel oxide, in saggers and in the presence of anthracite fines and dolomite in the ratio of approximately 20:5:1, could be converted to sponge nickel when heated to approximately 1,900° F. for about 2 to 4 hours, depending on the size and density of the oxide charge. The tests also determined the type of saggers suitable for pilot-plant operations.

Jan 1, 1959

By R. Barany

This paper reports determinations of heats of formation (from the oxides and elements) of crystalline cadmium metasilicate and crystalline lead meta-silicate by hydrofluoric acid solution calorimetry. The results, in conjunction with known entropy values, yield free energies of formation. There are no earlier data of this type for cadmium metasilicate. The results of this investigation for lead metasilicate deviate from the literature values (which are less reliable) in the direction of increased thermodynamic stability. Both cadmium and lead metasilicate are much less thermodynamically stable with respect to their constituent oxides than are the corresponding compounds of the alkaline earth metals.

Jan 1, 1959

By R. L. Montgomery

The literature has been surveyed and values recalculated for the heats and free energies of formation of solid rare-earth compounds at 298° K. In most instances it was necessary to estimate the entropies. Thermodynamic properties of aqueous rare-earth ions have also been calculated. INTRODUCTION The accumulation of thermochemical data on rare-earth compounds in recent years makes it possible to review the subject and to obtain more consistent and more reliable information than was available previously.

Jan 1, 1959

By J. F. Barkley

Field tests were made on the rate of corrosion of 30 materials used in air preheaters under regular operating conditions, and the buildup of deposits was observed. Twenty-three materials were tested with coal as the fuel on an underfeed stoker and seven with oil, including a short period with pulverized coal as fuel, The plant equipment is described, and pertinent plant operating data are tabulated. Figures 17 and 19 (pp. 24 and 27) give the results of corrosion tests on the uncoated metal test specimens. The information obtained from these tests follows the general pattern described in Bureau of Mines Report of Investigations 4996, Corrosion and Deposits in Regenerative Air Preheaters. The deposits were similar, and the corrosion rates of Cor-Ten and Mayari-R steel (previously found to be essentially the same at the Harding Street Station using coal) continued to show little difference at the Marion Generating Station using principally oil. The one high-alloy steel tested, type 321, showed a much higher corrosion rate than the low-alloy steel, Cor-Ten.

Jan 1, 1959

By T. M. Nasiatka

This report sterns from a study undertaken by the Federal Bureau of Mines to determine the possibility of reducing filter-cake moisture by applying radiant heat. Suitable laboratory equipment was set up to study the effect of heat, heating time, proximity of the heater to the filter cake, cake thickness, and other variables related to the final filter-cake moisture. A minus-48-mesh coal slurry and application of heat for 60 seconds resulted in filter-cake moistures 5.6 to 13.2 percentage points lower than could be accomplished by filtration alone at 24 inches of Hg for 1-1/4-and 1 1/2-inch cake thickness, respectively. The moisture reduction can be attributed to the combined effect of lower fluid viscosity and evaporation.

Jan 1, 1959

By H. S. Caldwell

A magnesium-base incendiary alloy, containing about 20 percent cadmium, 4 percent aluminum, and 0.5 percent zinc, was investigated in a series of vacuum-distillation experiments to determine the feasibility of recovering magnesium and cadmium as refined metals. Alloys prepared in the laboratory and actual bomb-casing alloy were studied at temperatures of 550° to 750° C. and pressures of 100 to 150 microns. Simple distillation and fractional distillation methods were only partly effective in separating the cadmium and magnesium. They were separated satisfactorily, however, with a special vapor baffle designed to condense the metals selectively. Magnesium and cadmium products were 99 percent pure and together comprised 82 percent of the total condensate. About 17 percent of the condensate was intermediate-grade alloy that could be recycled with new charge and contained about 70 percent magnesium and 30 percent cadmium.

Jan 1, 1959

By J. P. Coughlin

Gypsum plaster is calcium sulfate hemihydrate (CaS04-1/2H2O). There are two varieties, commonly designated as a and ß. The hydration setting) of this plaster involves the chemical reaction: CaS04?1/2H20(c) + 3/2H20(l) = CaSO4?2H20(c); that is, the hemihydrate combines with water to form the dihydrate. Many substances, when present as impurities, either in the hemihydrate or the water have influenced the rate of the hydration reaction. The objective of the Bureau of Mines work described in this report was to investigate the accelerating or retarding effects of small amounts of dissolved substances and to attempt to classify these effects upon a chemical basis. To eliminate competing effects, the work was conducted separately on the two varieties of hemihydrate; both were in highly pure form. (Commercial plasters usually are a mixture of the hemihydrates, with other substances present as impurities.) As the hydration reaction of each variety of hemihydrate evolves heat in amounts known from previous work, 5,6/ the authors decided to use calorimetric methods to follow the extent of the hydration reaction as a function of time. Two calorimetric methods were employed. One was designed to study the hydration reaction with a large water to plaster ratio and the other with a small water to plaster ratio (to simulate commercial practice in utilizing plaster).

Jan 1, 1959

By Alton B. Cook

Equipment has been designed and fabricated for study of the vaporization of oil during gas-cycling operations, A sand-packed steel tube, which can be rotated to minimize gravity drainage, is used as a model oil reservoir. A minute windowed cell at the discharge end of the tube through which the liquid-gas interface may be observed, makes possible the separate removal of produced free gas and gas-saturated oil. The operation of the model oil reservoir, and auxiliary equipment, are described by use of a schmatic flow diagram. Details of the specially designed equipment are illustrated by isometric and pictorial drawings, and a description of the experimental procedure is given.

Jan 1, 1959

By J. B. Gayle

The merits of the various methods for dry-quenching coke have been the subject of numerous publications and almost equally numerous controversies for the past 40 years.5/ Most investigators have concluded that dry quenching is advantageous. Some have based their arguments on the improved physical properties of the resultant cokes. Others have claimed little or no improvement and have based their arguments on the economies acquired from the recovery and utilization of sensible heat. The extent to which the method of quenching influences the properties of the resultant cokes is of importance in connection with the operation of both commercial and experimental ovens. On the other hand, the recovery and utilization of sensible heat are economic problems related solely to commercial oven operation and- depend on the method of dry quenching used and the demand for a low intensity energy source. The scope of the present Bureau of Mines investigation has been limited to a comparative study of the properties of wet- and dry-quenched cokes produced from six coals and blends carbonized at flue temperatures of 2, 000° and 2,400° F. in the Tuscaloosa oven.

Jan 1, 1959

By J. S. Tosh

An equilibrium study of the system potassium carbonate, potassium bicarbonate, carbon dioxide, and water has been conducted with solutions of 20-, 30-, and 40-percent equivalent potassium carboaate concentrations. These equilibrium data cover the operating range of the hot carbonate scrubbing system for removing carbon dioxide from gas mixtures. Such data are necessary to establish the limits of purification and are used to design absorption and regeneration towers. Values of K in the relationship K = (KHCO3)2/(K2CO3)PCO2 were determined for higher temperatures of 70" to 140° C. and greater concentrations, I 20 to 40 percent, than employed by previous investigators. For the 20- and 30-percent concentrations, K is constant at a given temperature; thus, once K has been determined the equilibrium pressure of carbon dioxide can be calculated for any conversion. Variation of & values with changing conversion was observed with the 40-percent solutions, so that equilibrium calculated pressures are less reliable from average K values.

Jan 1, 1959