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By A. Gene Collins

The Bureau of Mines undertook research to determine the bromide and iodide content of Mississippi and Alabama oilfield waters of the Tertiary and Cretaceous Period to determine genetic relationships of the ions, to determine their origin, and to determine their genetic relation to petroleum. The 280 samples were analyzed after a pretreatment to remove interferences. The iodide was oxidized to iodate and was titrated with thiosulfate. The bromide was oxidized to bromate and was determined iodometrically. A computer was used to calculate the correlation coefficients of iodide to bromide and to other ions. The other ions are sodium plus potassium, calcium, magnesium, chloride, bicarbonate, and sulfate. The mineral content of the samples ranged from 52 to 1,760 mg/l for bromide and from 2 to 65 mg/l for iodide. The mean bromide-to-chloride and iodide-to-chloride ratios were 0.0065 and 0.0002. The correlation coefficient matrix and linear plots indicated a definite bromide-to-calcium relationship for the brines investigated.

Jan 1, 1967

By G. L. Gates

The Bureau of Mines in cooperation with the City of Long Beach) Calif.) studied some physical factors effecting the deposition of barium sulfate scale in oil-well rotary pumps. Freshly formed barium sulfate was obtained by combining sulfate in sea water with barium from a barium chloride solution. The rate of scale deposition was measured quantitatively by weighing the pump impellers and diffusers. The results of the tests showed that coating the impellers with plastic significantly reduced the rate of barium sulfate deposition.

Jan 1, 1967

By Charles S. Allbright

This report describes hydrogenation of petroleum distillate fuels in bench scale equipment and the effects of hydrogenation on the storage stability and the composition of the fuels. Two distillate fuels were hydrogenated in laboratory equipment using a commercially available cobalt molybdate catalyst. Reactor temperatures were varied from 600° to 850° F and pressures from 100 to 600 psig. Product fuels were analyzed by ASTM, Bureau of Mines, mass, and infrared methods. Hydrogenation of a catalytically cracked fuel from Oklahoma crude oil significantly improved the storage stability, reducing insoluble gum formed during 9 months of storage at 110° F from 19.0 to 1.3 mg per 100 ml fuel, average. Conversion of the olefins to other hydrocarbon types varied with the temperature of hydrogenation--at 700° to 850° F the conversion was mainly to aromatics, at 650° F about 50:50 to saturates and aromatics, at 600° F principally to saturates. Processing a fuel composed of a mixture of virgin distillate and catalytically cracked stock, both from Illinois crude, at 700° F and 200 psig effected marked improvement in stability; the buildup of insoluble gum in storage was lowered from 18.3 to less than 1 mg per 100 ml fuel.

Jan 1, 1967

By E. G. King

The Bureau of Mines made experimental determinations of the heats of formation of forsterite and chrysotile at 298.15° K. The heat capacities of two polymorphs of serpentine, chrysotile and antigorite, were measured over the temperature range from 50° to 298° K and the entropies at 298.15° K were evaluated. The heat content of antigorite above 298.15° K was measured to 850° K. These thermochemical data were combined with other pertinent data to give heat and free energy of formation values at high temperatures. Free energy values are given for the reaction, forsterite + water = brucite + serpentine at different temperatures and pressures.

Jan 1, 1967

By V. R. Miller

The Bureau of Mines investigated methods for testing the tensile and sheer strength of cast specimens of bulk solder and of soldered joints in order to increase the strength and extend the useful temperature range of soft solders. A spread-area test for determining the wettability of solder on copper surfaces was developed. Mannitol was used as a flux in spread tests to control spreading and to avoid plating, etching, and other side effects of regular fluxes. Data on commercial and high-purity solders obtained by these methods show more consistency than those reported by others from similar tests.

Jan 1, 1967

By H. R. Babitzke

The purpose of this Bureau of Mine- investigation was to develop columbium and tantalum alloys suitable or u at elevated temperatures. Columbium and tantalum were combined with tungsten, hafnium, zirconium, molybdenum, vanadium, and titanium, and the resulting alloys were evaluated with respect to workability, hardness, electrical resistivity, strength at elevated temperatures, oxidation resistance, and weldability. Cb-33Hf-10W-10Ti, Cb-20111-5Mo, and Cb-30Hf-5Mo exhibited superior high temperature properties. Cb-33Hf-10W-10Ti had tensile strength values of 44,300 psi at 1,200° C and 16,500 psi at 1,400° C, Cb-20Hf-5Mo had values of 35,700 and 20,700 psi, respectively. The corresponding values for Cb-30Hf-5Mo were 38,900 and 17,800 psi. These alloys are fabricable by conventional methods with excellent strength at temperatures up to and including 1,400° C. An oxidation rate of 7 to 21 mg/cm2/hr was observed up to 1,000° C.

Jan 1, 1967

By Robert M. Becker

The evaluation of existing rock stresses from measurements of the change in diameter of a borehole that is stress relieved by overcoring has become a common practice, The stress evaluation has been generally based ,on isotropic relations whereas rock in varying degrees is anisotropic. A plane elasticity solution for a circular hole along one axis of an orthotropic medium is adapted for evaluation of in situ stress from borehole deformation measurements. A consistent triaxial testing approach for determining elastic properties of the overcore is also outlined. Comparison of isotropic with anisotropic interpretations of the state of stress show that large errors in evaluation may occur if the anisotropic character of the rock is neglected.

Jan 1, 1967

By Jr. Fish

As a part of a study of iron are resources in the Appalachians, 9 diamond drill holes aggregating 1,580.7 feet were drilled in a portion of the Butt Mountain area of northeastern Giles County, Virginia. Three hematitic sand-stone beds were intersected in the Clinton formation but only one was consistent in thickness and grade in all 9 drill holes. This bed averages 18.9 percent iron over an average thickness of 24 feet. The drill cores were logged and chemical analyses were made on 161 individual samples and 22 composite samples. Beneficiation studies were made of three composite hematitic sandstone samples each representing a separate bed containing 14.6, 19.8 and 20.0 per-cent iron. Major mineral constituents of the samples were hematite, quartz, and sericite.

Jan 1, 1967

By Henry M. Harris

A study was made by the Bureau of Mines to determine if shapes of oxide-glass compositions could be roll-formed at high temperatures, and to find the conditions required for adequate formability. A unit with directly connect' furnaces and heated rolls that allowed forming of most of the compositions developed. Glasses of the feldspar type were chemically unreactive with the alumina grains, and allowed the best roll forming. Optimum forming was attained at temperatures of 1,400° to 1,530° C, with compositions containing 30 or 40 percent feldspar and 60 or 70 percent alumina. Formability was better when compositions contained minus 325-mesh materials, rather than coarser or finer powders. In many cases, roll-formed shapes had physical properties equal to or better than the normally sintered shapes of the same composition.

Jan 1, 1967

By Jack L. Henry

The monocarbide region of the ternary system U-C-O has been investigated at 1,700° C as the first phase of a more extensive study of a portion of the four-component system U-C-O-N. An area bounded by the following compositional limits in atomic percent was studied: U, 44 to 55; C, 30 to 60; 0, 0.2 to 20. Compacts composed of mixtures of uranium, graphite, and uranium dioxide powders were sintered at 1,700° C under an equilibrium pressure of carbon monoxide to produce uranium oxycarbide specimens having a variety of compositions. Sintered specimens were evaluated by X-ray, chemical analysis, and ceramographic techniques. Solid-solution boundaries and phase relations have been established, and the effects of composition on the lattice parameter as well as the decomposition pressure have been investigated. Oxygen can be substituted for carbon in stoichiometric uranium monocarbide to the extent of about 17 atomic percent at 1,700° C. The composition range of the oxycarbide solid solution extends from about 48 to 51 atomic percent uranium in the low oxygen region. Above 10 atomic percent oxygen the composition range narrows to less than 1 atomic percent uranium. Carbon monoxide exists as a gaseous phase in equilibrium with all compositions which contain oxygen. Five separate phase fields were found bounding the solid-solution area. Other phases within this portion of the system include uranium, uranium dioxide, uranium dicarbide, and uranium sesquicarbide. Decomposition pressures of oxycarbide compositions at 1,700° C have been found to vary from a few microns for stoichiometric and uranium-rich compositions to 35 torr for carbon-oxygen-rich specimens. Lattice parameters were found to depend upon the U to C + 0 ratio as well upon the extent of substitution of oxygen into the stoichiometric monocarbide lattice.

Jan 1, 1967

By R. B. Tippin

The heavy liquid separation (HLS) process was investigated by the Bureau of Mines to develop a means of concentrating minerals from natural ores, Various spodumene ores were tested in a 0.4-inch diameter cyclone using pure tetrabromoethane (TBE) as the heavy liquid. Studies were initiated to examine the influence of (1) pulp density (2) feed grade, (3) cyclone pressure, (4) cyclone apex opening size) (5) cyclone vortex finder opening sand (6) mineral particle size on the separation efficiency. Each of these factors was found to affect the heavy liquid separation in some degree; the mineral particle size exhibited the greatest effect and the ore feed grade the least. Conditions necessary to yield an 85 percent spodumene concentrate with an 85 percent recovery were determined to be: 70 psig pressure, 10 percent solids, 0.08-inch apex opening, 0.11-inch vortex finder opening and a minimum amount of minus 200-mesh fines in the feed. Operation of multiple cyclones in series resulted in spodumene concentrates assaying over 90 percent and indicated mineral recoveries exceed-in 90 percent.

Jan 1, 1967

By R. L. Hopkins

Some typical thiacyclopentanes and thiacyclohexanes were synthesized to provide reference compounds needed for the identification of sulfur compounds in crude oils. Two general methods of synthesis were employed: (1) cleavage of 2-alkyltetrahydropyrans with hydrogen bromide followed by the reaction of the resulting dibromoalkanes with sodium sulfide and (2) the catlyzed reaction of cyclic ethers or 1)4-or 1)5-alkanediols with hydrogen sulfide. Both methods produced mixtures of 2-alkylthiacyclopentanes and 2-alkylthiacyclohexanes with 2-alkyltetrahydropyran as the starting material. The structures of the reaction products were established by analysis for sulfur; desulfurization; gas-liquid chromatography (GLC); mass, infrared, and nuclear magnetic resonance (NMR) spectra; and an alternate synthesis. The synthesis of the cyclic sulfides contributed substantially to the identification of 10 members of this class of sulfur compounds in crude oil.

Jan 1, 1967

By K. P. V. Lei

The Bureau of Mines investigated molten salt electrorefining 'n helium atmosphere cells as a means for the production of ductile vanadium. 'Electrolytes composed of NaCl-VCl2, LiCl-NaCl-VCl2, BaCl2-KCl-NaCl-VCl2 KCl-LiCl-VCl2, and CaCl2-NaCl-VCl2 were tested. Two electrolytes, KCl-LiCl-VCl2 and CaCl2-NaCl-VC12, were selected for laboratory-scale production tests. A molten salt electrorefining process was developed for the production of ductile 99.6 percent vanadium from a commercial 90-percent grade. Using the CaCl2-NaCl-VC12 electrolyte, an 87-percent recovery of ductile vanadium was made; an 85-percent recovery was made with the KCl-LiCl-VCl2 electrolyte.

Jan 1, 1967

By J. G. Walters

This report presents the results of an investigation in Which the chloroform solubilities of coals and chars are related to rank, temperature of thermal treatment, time at a given temperature, vacuum thermal treatment, plasticity, oxidation, blending, and mass spectral analyses and molecular weights of the extracts. It was found that the quantity of chloroform extract obtained from chars can be altered by creating a vacuum above the charge during preparation of the char, increasing the time at temperatures within the plastic temperature range, and by utilizing different rates of heating to attain a given temperature. Relationships found between the chloroform solubilities of chars produced at temperatures within the plastic temperature range and the relative fluidities in this temperature range indicate that the chloroform-soluble portion of the char is a significant component of the plastic mass. Chloroform-extract yields from chars made from blends of coals cannot be calculated from chloroform-extract yields obtained from chars made from the component coals.

Jan 1, 1967

By J. L. Shultz

The Bureau of Mines extended its investigation of methanation catalysts. The noble metals (platinum, palladium, ruthenium, rhodium, osmium) and rhenium), molybdenum, and tungsten were tested in hydrogenations of carbon monoxide and carbon dioxide at 21 atmospheres in a temperature range between 200° and 600° C. From the 8 metals studied) 25 catalysts represent 5 catalyst types were prepared and tested. The impregnated 0.5-percent-ruthenium catalyst proved to be the most active and versatile of all the catalysts produced. Tungsten and the noble metals other than ruthenium were low in activity and usually required temperatures above 500° C for appreciable production of hydrocarbons. Molybdenum was moderate in activity, but further improvement in molybdenum catalysts seems possible.

Jan 1, 1967

By Hillary W. St. Clair

The reduction zone of the iron blast furnace is represented by a mathematical model of the chemical reactions and heat transfer that occurs between gas and solids during the deoxidation of iron oxide. The model consists of a set of equations and an algorithm whereby the equations may be solved to give the temperature and composition of gas and solids at any position in the reaction zone and at any time after a specified initial state. The model is applied to the special case in which ferric oxide is reduced by graphitic carbon and carbon monoxide produced by burning carbon in dry air. The rate of reduction, carbon consumption and maximum temperature are shown as functions of the temperature and rate of flow of the incoming reducing gas and external heat loss. The model of the reduction zone is the essential part of a general mathematical model for simulation of the iron blast furnace. The simulation model will serve as a research tool to be used in conjunction with an experimental or operating furnace. After the simulation model has been correlated with the real furnace, it is proposed that further experimentation be done mostly with the model. The real furnace will then be operated primarily to test and confirm the model.

Jan 1, 1967

By R. T. Sorensen

Bench-scale and continuous testing were performed to adapt the anionic process for flotation of calcium activated silica to the fine-grained hematitic-goethitic jaspers from the Marquette range, Michigan. These ores typically contain about 35 percent Fe and require grinding to about 80 to 100 percent minus 400 mesh to insure an adequate liberation of gangue from the iron oxides. A method for removal of troublesome slime fractions without excessive iron loss, by first dispersing the quartz and then selectively flocculating the iron oxides, was evolved in the laboratory and successfully accommodated to pilot plant practice. The efficiency of the flotation process was improved with respect to both reagent usage and concentrate grade and recovery by using the selective flocculation-desliming technique as a pretreatment. The benefits of the combined desliming-flotation procedure were most evident in pilot plant processing. The best tests on two ores yielded recoveries of about 84 percent in concentrates containing 65.1 percent Fe and 4.8 percent SiO2 and 66.2 percent Fe and 3.9 percent SiO2, respectively. These results are in comparison to recoveries about 10 percent lower than the above to concentrates containing 63.9 percent Fe and 6.6 percent SiO2 in the one instance, and 63.6 percent Fe and 7.2 percent SiO2 in the other, obtained by flotation without the prior desliming treatment.

Jan 1, 1967

By R. J. Leary

The Bureau of Mines experimental blast furnace was blown with oxygen-enriched blast in combination with natural gas injected at the tuyeres. The air blast was augmented with oxygen to form an enriched blast containing 24,8 pct oxygen, and tests were run at natural gas injection rates of 4.5, 6.0, and 8.3 pct of the air blast. Similar enrichment to 26.8 pct oxygen was tested at natural gas rates of 7.2, 9.1, and 11,0 pct of the air blast. At intermediate proportions of natural gas to oxygen, (1) the fuel rate and the replacement ratio of coke by natural gas were unaffected by oxygen injections and (2) the productivity increased about 4 pct for each I pct oxygen added to the blast. The higher proportions of natural gas to oxygen were less efficient; in return for a lower coke rate, the fuel rate increased and productivity declined. A deficiency in reducing gas imposed a limit upon lower than normal proportions of natural gas to oxygen. Beyond this limit the formation of reducing gas was insufficient to support the rate of metal production. When this condition was encountered, the coke rate requirement for specification iron was abnormally high and production fell off badly. Adiabatic flame temperature is discussed as a means for proportioning oxygen and natural gas additions.

Jan 1, 1967

By C. A. Komar

The Bureau of Mines conducted experiments on one synthetic and three natural sandstone samples to investigate the effects of acoustic energy on the flow of brine in porous media. Ultrasonic energy at a frequency of 20 kc per second and an intensity of 55 watts per cm2 was irradiated in the direction of the fluid flow and in the opposite direction for distances of 1/2 and 2 inches between the vibrating device and the sample face and under conditions of suppressed and nonsuppressed cavitation. Forty tests were conducted: 32 with a pressure differential of 0.64 psi across the samples, 2 with 5 psi, and 6 with 15 psi. Acoustic waves altered the rate of flow of the brine through the samples, but this effect was observed only at low differential pressures and from a practical point of view was insignificant. As a result of irradiation, however, the samples exhibited reduced permeability. This reduction was probably caused by the shifting of solid particles dislodged by the acoustic waves.

Jan 1, 1967

By John E. Miller

Absolute viscosity values for gases usually are determined with a capillary tube viscosimeter, One of the correction factors applied to the experimental data is that for nonuniformity of the capillary bore. This report contains useful analytic expressions of the nonuniformity correction for the following cases: ellipse, cone, sine wave, sawtooth wave, square wave, and the general case. The methods herein described are applied to estimate the nonuniformity of a section of stainless steel capillary tubing to be used at the Bureau of Mines Helium Research Center. Several other examples are given to illustrate the usefulness of the present results.

Jan 1, 1967