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By M. G. Zabetakis

This publication describes an investigation conducted by the Federal Bureau of Mines regarding the cause of an explosion of a dephlegmator or fractionating column at the Cities Service Oil Company Refinery, Ponca City, Okla., January 22, 1959. The column was that used with the refinery's No.1 Dubbs Coker. The explosion caused the death of an employee of the refinery and resulted in extensive damage to the refinery and to nearby property. The Bureau's study of the explosion began January 26.

Jan 1, 1960

By D. Bienstock

The Fischer-Tropsch synthesis is practicable in a reactor where the exothermic heat of reaction is removed by circulating large quantities of recycle gas through a catalyst bed of high-voids content. At an hourly space velocity of 1100, the feed gas, a mixture of 1.5 parts hydrogen to 1 of carbon monoxide, was converted 90 percent, producing hydrocarbons predominantly in the gasoline range. At these conditions a recycle-to-fresh gas ratio of 40:1 was enough to give excellent temperature control with a pressure drop of 1.5 p.s.i. per foot of bed using a steel catalyst in the form of lathe turnings. Steel parallel plates, although offering lower resistance to gasflow, were less reactive and less durable. INTRODUCTION The Federal Bureau of Mines has been engaged in a research and development program since 1944 on the synthesis of gasoline from coal. Gasification of coal with steam and oxygen to yield a synthesis gas--a mixture of carbon monoxide and hydrogen--is being investigated at Morgantown, W. Va.; and the synthesis of gasoline by catalytically reacting the carbon monoxide and hydrogen over iron by the Fischer-Tropsch reaction is being investigated at Bruceton, Pa.

Jan 1, 1960

By J. L. Konchesky

The technical feasibility of gasifying powdered, noncoking, low-rank coal with steam in an externally heated tube has been demonstrated. The tube, 112 ft. of alloy-steel tubing shaped into a helix, served as an electrical conductor of electricity used for heating. The effects of the following variables were studied: Residence time of coal in reactor, average reaction temperature, steam concentration, and rank or geologic age of coal. Reaction pressure was maintained in the range 19-26 p.s.i.a. High carbon conversions and large yields of synthesis gas were obtained with low-rank coal. In one test, for example, about 88 pct. of the carbon in a subbituminous C coal was gasified at 1,910* F. with a residence time of 1 sec. The gas contained 58 pct. H2, 19 COD 15 CO, and 3 CH4; the yield was 30 cu. ft. (at 32' F. and 14.7 p.s.i.) of synthesis gas (CO + H2) per pound of dry coal.

Jan 1, 1960

By M. G. Zabetakis

The use of liquid hydrogen as a high-energy fuel introduces numerous hazards not ordinarily associated with the use of other more conventional fuels. These hazards are attributable to the unique properties of hydrogen in the liquid and gas states (table 1). Since little work has been conducted on explosion and related hazards of cryogenic fuels, a research program was undertaken to obtain basic data on such dangers for hydrogen and other combustibles under these conditions. These data were used to outline emergency procedures for protecting personnel and equipment when an accidental spillage of liquid hydrogen occurs and to establish a quantity-distance table for the storage of this fuel. The vaporization of liquid hydrogen from a surface is treated as a prob¬lem in heat transfer theory. Two extreme cases are briefly considered: (1) The transfer of heat occurs at constant temperature drop between, the boiling liquid and the hot surface, and (2) the transfer of heat is limited by the rate at which it can flow to the surface from a hot insulating medium. The available data indicate that the former case (1) is applicable when vaporizing from a conducting surface and, initially, when vaporizing from an insulating medium; the latter case (2) is applicable after initial flash vaporization has occurred from the insulating medium. The vaporization rate determines in part the rate at which flammable hydrogen vapor-air mixtures are formed above a spill area. However, the rates at which heat is transferred to the vapor, and air is brought in contact with it also are of importance. Accordingly, the distribution of flammable mixtures above a spill area was determined experimentally. In general, flammable mixtures were found to be both above and within the visible vapor cloud.

Jan 1, 1961

By A. D. Hahn

The Federal Bureau of Mines examined ilmenite-bearing sands in southern Texas as part of a program to discover sources of supply for the domestic titanium industry. Deposits were examined from May 1956 through January 1959 in the outcrops of sandstone beds in the Jackson group of Eocene formations in Lee, Burleson, Fayette, and Starr Counties on the Gulf Coastal Plain; in alluvial valley fill in Brewster County in southwest Texas; in the sand beaches of Matagorda Peninsula and the Galveston, Padre, and Brazos Islands--part of the offshore chain of barrier islands along the Texas coast; and in unconsolidated sediments in Willacy County on the Rio Grande delta in the southeast Texas.

Jan 1, 1961

By A. D. Hahn

This report describes reconnaissance by the Federal Bureau of Mines of titanium-bearing sandstone in Kemper County, Miss. The purpose was to determine the ilmenite, rutile, and associated heavy-mineral content of black-sand-bearing Eocene deltaic formations" 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 (Ti02), titanium oxide, is used mainly in producing welding-rod coatings and titanium metal. The fieldwork was conducted during the first half of November 1959. Seven holes, totaling 304 feet of bore, from which 64 samples of cuttings were taken, were drilled in the north-central part of the county; and two holes, totaling 172 feet of bore, from which 34 samples of cuttings were taken, were drilled in the southeastern part.

Jan 1, 1961

By Paul L. Campbell

Investigations by the Federal Bureau of Mines of methods of upgrading tar obtained by low-temperature carbonization of lignite showed that ß,ß?-oxydipropionitrile, ß,ß?-iminodipropionitrile, and ß,ß'-thiodipropionitrile were effective solvents for extracting aromatics (aromatic hydrocarbons plus polar compounds) from coal-tar neutral distillate fractions. Batch extraction showed that these solvents extracted approximately the same percentage of aromatics from various neutral oil fractions boiling between approximately 170° and 350° C. In continuous countercurrent extractions using oxydipropionitrile and iminodipropionitrile, approximately 30 to 35 vol.-pct, and 65 to 70 vol.-pct, of the aromatics in 170° to 350° C. neutral distillate oil were extracted at room temperature when solvent-to-oil ratios were 2:1 and 12:1, respectively. As the concentration of aromatics in the neutral distillate oil fraction decreased, the capacities and, to some extent, the selectivities of these solvents for the remaining aromatics decreased. Aromatics were isolated from the extracts and the solvents recovered by washing the extract fractions with a low-boiling paraffinic hydrocarbon such as heptane, using hydrocarbon-to-extract ratios of at least 2:1. The heptane wash removed most of the aromatics but only part of the polar compounds (compounds containing oxygen, sulfur, and nitrogen) from the extracts. The recovered oxydipropionitrile and iminodipropionitrile, containing polar compounds, were effective in extracting aromatics from neutral distillate oils. The contaminated solvents showed essentially the same capacities and selectivities as the pure solvents.

Jan 1, 1961

By J. J. Demeter

Experiments were conducted in 2- and 4-inch-diameter standpipes to evaluate the effectiveness of standpipes as pressure seals. During the experiments, these standpipes conveyed Alan-Wood magnetite (60 to 230 U.S. standard sieve mesh) by gravity flow from one vessel to another of relatively higher pressure. The information obtained has been helpful in a Federal Bureau of Mines investigation of how to make either synthesis gas or hydrogen by a modified steam-iron process employing a continuous recycling stream of granular iron-iron oxide at temperatures of 600° to 900° C. In this process the mixture of granular material flows by gravity from a reduction vessel at low pressures to an oxidation vessel at higher pressures. Data from the 2- and 4-inch-diameter standpipes indicate that it would be practical to use a standpipe as a pressure seal between the reductor and oxidizer. Investigators found that, by gravity flow, the standpipe could convey the Alan-Wood magnetite against pressure gradients up to 1.07 pounds per square inch per foot of column height.

Jan 1, 1961

By W. A. Calhoun

The purpose of this investigation was to develop economical mineral dressing processes for removing objectionable quantities of impurities, such as quartz and pyrite, from refractory clay deposits in east central Missouri. The presence of excessive quartz in these clays causes crazing. Pyrite causes bloating and unsightly dark blobs on the surface of fired refractory brick. The iron concentration in the proper state of oxidation may also act as nucleation centers for carbon crystal growth which can result in bursting of the refractory. Numerous deposits, representing a very large tonnage, have been examined and prospected by various refractories companies and found to contain impurities in objectionable quantities. Upgrading these clays would greatly extend our reserves of high-quality refractory clays. Wet-tabling and wet-cyclone concentration were found to be effective for removal of impurities from clays. Of the two methods, wet-cyclone concentra¬tion would be cheaper and more effective. Although wet-tabling improved the refractory properties of each clay, beneficiation by wet-cyclone produced clays of superior quality. Clay recoveries by wet-cycloning ranged from 56.1 to 81.8 percent of the weight of the crude samples, and the beneficiated clays contained from 71.9 to 94.4 percent of the total alumina. The pyrometric cone equivalent (PCE) was increased from 1 to 3 cones by wet-cycloning. The beneficiated clays also met the reheat shrinkage requirements on refiring to 1,400° C. Missouri is one of the major domestic sources of fare clay. In addition to deposits of high-grade refractory clays, there arc many deposits that contain small percentages of impurities, which render the clays unfit for the production of high-heat-duty firebrick. Development of methods to beneficiate these submarginal clays to usable materials would greatly increase commercial fire clay resources.

Jan 1, 1961

By W. L. Hunter

The research on this report was conducted to obtain information on the feasibility of producing ferro chromium of varying silicon and carbon contents from domestic chromite. Concentrates from the Mouat deposit were chosen because they typify the chromite found in the Stillwater complex, the largest domestic reserve, and are similar in composition to other extensive North American and foreign deposits. Batch-smelting tests designed to produce high-, medium-, and low-carbon ferrochromium were made in single phase and three-phase, electric-arc, steelmaking furnaces. Agglomeration studies were made in a rotary kiln. Continuous smelting tests were made to yield data on the production of high-carbon ferro chromium and low-carbon ferrochromium-silicon. The carbon content of high-carbon ferrochromium was lowered to the medium-carbon range by oxygen injection. Mouat stockpile concentrates were nodulized in a gas-fired rotary kiln using quartz, limestone, and fluorspar additions in the proportion necessary to flux the slag. The nodules were smelted in a continuous test using coal, coal char, and mixtures of the two consecutively as reductants.

Jan 1, 1961

By R. S. McClain

The Federal Bureau of Mines investigated residues from aluminum plants, to determine if carbon could be removed by flotation while recovering fluorine and aluminum compounds for recycling to the reduction process. This publication summarizes studies on samples representing three types of plant waste products, supplied by three aluminum-producing companies. Samples of flue dust, pot skimmings, and pot linings from the various plants all responded to a simple turpentine flotation scheme to reject 90 to 97 percent of the carbon. Aluminum compound recoveries ranged from 42 to 94 percent on the flue dust, were about 95 percent on the pot skimmings, and ranged from 75 to 89 percent on the pot linings. Fluorine recoveries from the same samples ranged from 35 to 63, 92 to 95, and 77 to 86 percent, respectively. The pot linings contained soluble salts of aluminum and fluorine which were recovered by precipitation with sodium aluminate and carbon dioxide gas. Composites of residues from each plant responded to flotation much the same as the individual samples. Aluminum is produced by the electrolysis of alumina in a molten cryolite bath. The electrolytic reduction cell consists of a carbon-lined box containing a pad of molten aluminum which serves as a cathode, a carbon anode, and an electrolyte of molten cryolite in which the alumina is dissolved. Alumina is reduced to aluminum at the cathode, and carbon is oxidized at the anode.

Jan 1, 1961

By M. A. Hammer

In this study by the Federal Bureau of Mines Pennsylvania anthracite from the Eastern Middle field was oxidized by concentrated nitric acid at steam-bath temperature for 24 to 1,000 hours. The quantitative data obtained include yields of nitric-acid soluble and insoluble products and the distribution of carbon and ash in each. The acid-insoluble residues were examined for solubility in aqueous sodium hydroxide. With a sodium hydroxide concentration of at least 1 normal, a portion of the residue could be extracted in the form of a true solution. With lower alkali concentrations, peptization occurred. Alkali solubility of the residue increased with length of oxidation. However, when expressed in percentages of original coal weight, the alkali solubility remained essentially constant after 192 hours of oxidation. This suggests that the alkali-soluble products are converted to acid-soluble products at the same rate as the original coal substance is converted to alkali-soluble material. Microscopic observations of the peptization of the acid-insoluble residues revealed a gross micellar physical structure. The action of nitric acid is apparently not restricted to the surface of a coal particle. The acid penetrates the particle through the pore structure, dissolving some of the ash and altering the bonds between the coal micelles. The bond alteration, as indicated by ultimate analyses, involves the physical and chemical adsorption of the components of nitric acid. Some of the altered bonds are not thermally stable; this instability is shown by the complete loss of peptizing ability when the acid-insoluble products are heated above 200° C. This loss is accompanied by the evolution of water, oxides of nitrogen, and hydrocyanic acid.

Jan 1, 1961

By F. P. Haver

The Federal Bureau of Mines developed a 10,000-ampere cell to determine the economic feasibility of producing high-purity electrolytic titanium from mill scrap or offgrade sponge. Operating variables were investigated, matetial handling procedures were established, and the cost of electrorefining titanium was determined. The prototype cell produced premium-grade metal (<100 Brinell hardness number (B.h.n.)) from very impure Kroll sponge at a processing cost of less than $0.60 per pound. Refined metal was deposited at the cathode in the form of coarse (85 percent plus 34-mesh), hexagonal crystals of a titanium when the cell was operated an 850° C. A cathode current density of 1,000 amperes per square foot and a molten sodium chloride electrolyte containing approximately 5 percent by weight of soluble titanium were used. In continuous operation, at the optimum number of ampere-hours, (40,000), the current efficiency averaged slightly less than 60 percent. It was possible to supply large enough amounts of electric current for electrolysis to maintain the temperature of the bath, thus reducing overall power consumption to less than 5 kilowatt-hours per pound of metal refined.

Jan 1, 1961

By J. L. Konchesky

In gasifying pulverized coal with steam and oxygen, the particle size of the coal fed to a gasifier should be as small as economically possible. A potential way to achieve this advantage is to reduce the particle size of the coal by passing the coal-steam mixture at high velocity through a heated tube coil before the mixture enters the gasifier. To evaluate this method the Federal Bureau of Mines flashed coal-water slurries in externally heated metallic tube coils to determine the extent of size reduction. The first of two different laboratory-scale apparatus reduced the average particle diameter of subbituminous C coal from 190 to 110 microns at an outlet velocity of 330 feet per second (f.p.s.). At the same outlet velocity, a second apparatus reduced the average particle diameter from 250 to 140 microns. An increase in velocity produced more finely divided coal, but variation in temperature and pressure had no effect except as they affected velocity. Virtually the same size reduction was noted for five ranks of coal at equal velocities. The rate of increase in particle-size reduction with increase in velocity decreased with a decrease in particle size. The pulverizing mechanism was concluded to be abrasion of the particles with each other and with the tube wall.

Jan 1, 1961

By T. A. Sullivan

The work described in this report was undertaken to evaluate and develop techniques for determining the oxygen content of titanium and titanium alloys. Early investigations of volatilization techniques involving halogenation were unsuccessful. Later efforts were concentrated on evaluating vacuum fusion and inert-gas fusion techniques. Two vacuum fusion methods and an inert-gas fusion method were found to be satisfactory in the 0.02 to 1.00 pct., oxygen range. These methods are described in detail. The coefficient of variation by any of the three methods is approximately 5 pct, While the main portion of this paper is devoted to the vacuum and inert-gas fusion methods, a resume of other suggested methods for analyzing titanium for oxygen also is given. INTRODUCTION The Federal Bureau of Nines has conducted research on titanium metal since 1938. This research included development of the Kroll process for the production of titanium (2)4, various sodium reduction processes for making titanium metal and lower valent titanium chloride-sodium chloride mixtures (17), and a fused salt electrolytic process for Me production of high-purity titanium metal and the recovery of titanium by electrorefining from off-grade materials (20).

Jan 1, 1961

By Joseph A. Sutton

This study was undertaken by the Bureau of Mines to determine whether the sulfur-oxidizing bacterium Thiobacillus thiooxidans could use sulfur compounds to produce sulfuric acid in sufficient quantities to leach valuable metals from low-grade ores. The results of extended tests indicated that the bacterium is capable of extracting appreciable amounts of copper and cobalt from ore and mineral samples when sulfur is available in a state that can be readily assimilated by the organisms. Under the conditions of these tests, this organism was not able to assimilate and oxidize the sulfur as it occurred in the ores and minerals. Ores containing copper minerals in the silicate, carbonate, and oxide forms, in the presence of elemental sulfur, were more susceptible to bacterial action than ores containing copper minerals in the sulfide form. Thiobacillus thiooxidans remained active on elemental sulfur in the presence of some of the ores which were tested, but could not tolerate others. Therefore, strains of the bacterium were progressively adjusted to increasing concentrations (0.5 to 10 grams) of the individual ores until they could remain active on 10-gram portions of all ores being tested.

Jan 1, 1961

By W. S. Sanner

Anthracite was used extensively as a fuel in iron metallurgy from 1840 to 1880. In 1874, 226 of the 680 blast furnaces in the United States were operating on anthracite and producing almost one-half of the Nation&apos;s pig iron. However, by 1890, railroad expansion, the development of western iron-ore reserves, and the growing use of coke decreased the importance of anthracite as a metallurgical fuel. As a result, the last blast furnace designed exclusively for anthracite use was built in 1891. Because of the increased energy requirements of our expanding national economy, the abnormally high demands during national emergencies, and the proximity of anthracite deposits to eastern steel-producing areas, interest has grown in again using anthracite in iron metallurgy. Estimates of anthracite reserves indicate a 300-yr. supply at a production rate of 30 million tons per year. These large reserves dictate the development of an adequate technology for the use of anthracite by the metallurgical industry.

Jan 1, 1961

By J. R. Nettle

The purpose of these studies by the Federal Bureau of Mines was to determine the feasibility of refining low-grade hafnium by an inert-gas-shielded molten-salt electrorefining technique to produce a hafnium metal meeting reactor specifications. The techniques were adapted from those used success-fully for titanium electrorefining. Three electrolytes containing hafnium chlorides were developed from which deposits having a Brinell hardness of 170 or below were recovered. A KC1 + NaC1 + HfC14 electrolyte produced deposits in the hardness range of 140 to 165 Brinell. Deposits with a hardness range of from 132 to 152 Brinell were pro-duced from an electrolyte composed of KC1 + LiC1 + HfC14. A third electrolyte composed of NaC1 + K3HfC17 produced deposits with a hardness as low as 139 Brinell. In a fourth electrolyte, composed of NaC1 + K2HfF6, a measure of refining was accomplished, but under the test conditions no metal meeting specifications was recovered; none was softer than 174 Brinell. A number of metallic impurities were reduced in quantity by the electro-refining process, notably iron, which normally was reduced from 250 p.p.m. to less than 50 p.p.m. Magnesium generally was reduced from 680 p.p.m. to less than 80 p.p.m. Manganese content was also reduced by the electrorefining process. Sponge containing 90 p.p.m. Mn yielded deposits containing a maximum of 50 p.p.m.; some deposits contained only 10 p.p.m.

Jan 1, 1961

By R. J. Leary

Iron and steel scrap has accounted for 45 to 50 percent of the metallics used by the steel industry. In an electric furnace which utilizes a 100-percent cold charge consisting of about 99 percent scrap and 1 percent pig iron, sensible heat from molten pig iron is not present as it is when hot metal is charged to open hearths and converters. A study of means for more efficient utilization of iron and steel scrap in steelmaking indicated that the time and fuel requirements to melt scrap were important cost factors, particularly in arc-furnace steelmaking. A process to preheat scrap economically prior to charging into the arc furnace has been developed, utilizing efficiently the heat from combustion of fossil fuels as a substitute for electric-arc heating in the initial stage of arc-furnace steelmaking. Scrap is loaded into a portable vertical cylindrical furnace body that is open at the top and has a perforated dropout door at the bottom. In the heating operation, the furnace body containing scrap is placed upon a hollow base connected to a flue, and then the burner and combustion-chamber unit is lowered on top of the furnace body. The stream of hot-combustion products flows down through the bed of scrap imparting heat to it, and the cooled gases exhaust through the flue. After the heating operation the furnace body containing hot scrap is transported to the arc furnace for charging. Thus, the furnace body serves as a charging bucket for top-charged arc furnaces, enabling this preheating process to be integrated into existing material-handling patterns in many arc-furnace plants.

Jan 1, 1961

By H. E. Peterson

Rhenium occurs in very small quantities (12).4 In order for the Federal Bureau of Mines to conduct an investigation of rhenium sources and methods of extraction, it was necessary to devise improved techniques for detecting and measuring minute quantities of the metal. A modification of the procedure of Malouf and White (46) was developed which can be used to detect rhenium in concentrations as small as 0.1 part per million and can be used to measure quantities of 1.0 part per million. It can be used for the analysis of siliceous and calcareous ores, of molybdenite concentrates, of fumes, of flue dusts, and of other metallurgical products. Development of the method involved devising an amine extraction procedure for separating rhenium from all interfering elements except tungsten and a selective distillation procedure for separating rhenium from tungsten. Adoption of these separation procedures permits use of large samples and precise determination of rhenium by colorimetric analysis of the thiocyanate complex of rhenium by means of a spectrophotometer.

Jan 1, 1961