Search Documents

By A. Gene Collins

Rapid, sensitive, and precise methods of determing major, minor and trace constituents of oilfield brines are needed. Several methods have been developed or adapted by the Federal Bureau of Mines at the Petroleum Research Center, Bartlesville, Okla. The following methods are described in this report: Spectrophotometric and volumetric for iodides and bromides; potentiometric for pH, alkalinity, acidity, borate boron, total boron, and organic boron; gravimetric for potassium; disodium ethylenediaminetetraacetate (EDTA) volumetric for total hardness, calcium, and magnesium; spectrophotometric for fluorides; and color comparison .for arsenic. Adequate sensitivity, precision, and accuracy were obtained for each method. The Bureau of Mines pioneered in research on the analysis of oilfield waters (2, 46, 47).6 However, several of these early procedures were quite time consuming. Also, they did not include methods for determining trace and minor constituents of brines.

Jan 1, 1961

By Robert K. Koch

The reactions of alumina and alumina monohydrate with wet hydrogen fluoride gas were studied by the Federal Bureau of Mines to determine the feasibility of producing commercial-grade aluminum fluoride from offgases generated by pyrohydrolysis of siliceous fluorspars. The test results showed than an aluminum fluoride reactor operating at maximum efficiency could retain 96 percent of the fluorine contained in off-gases generated by pyrohydrolysis of siliceous fluorspar. The requirements are a reactor temperature of 200° C. and a reactor entrance gas containing 5 mole-percent hydrogen fluoride. Partial pressure equilibrium constants were determined for the reaction of alumina monohydrate and wet hydrogen fluoride gas from 200° to 350° C. and for the reaction of alumina and wet hydrogen fluoride gas from 350° to 700° C. Both reactions are reversible, and they proceed in directions that are dependent upon the temperature and the relative HF:H2O concentration. Logarithms of the equilibrium constants were used to plot the reaction isobars; these can be used to calculate the theoretical maximum efficiency of a reactor processing wet hydrogen fluoride gas between 200° and 700° C. The theoretical maximum efficiency decreases with increasing temperature.

Jan 1, 1961

By Perry D. Teitelbaum

In two earlier studies the Federal Bureau of Mines undertook to explore comprehensively the dimensions of the Nation's energy balance. The first of these studies, published in 1950 as Bureau of Mines Information Circular 7582, by Harold J, Barnett, was primarily concerned with projections of future domestic energy requirements and supplies, because these related to projected growth in major fuel-consuming sectors of the economy, changing rates of energy-use efficiency, and interfuel substitution patterns. But, to provide the essential background for these projections, it was first necessary to assemble and examine in some detail the quantitative information on the size and shape of the current United States fuel economy. Among other things, Barnett's path-breaking study indicated the need to consider energy as an entity, particularly for public and private policy makers, industry and commodity analysts, economists, and others concerned with long range questions of domestic and international energy supply and demand. The study also spotlighted a gap in the fabric of current economic intelligence; no comprehensive collation and reconcilation in any single report of available published statistical information covering the origin -a disposition of all energy materials existed. In response to this latter need, the Bureau of Mines prepared the second of the two studies referred t3 above. This was published in 1951 as Report of Investigations 4805, by W, H, Lyon and D, S. Colby, and it consisted of statistical information on the production and use of each of the various fuels and electric energy in the United States for 1929, 1939, and 1947; all were presented in tabular form and on a uniform basis. The three years selected were chosen largely on the basis of data availability.

Jan 1, 1961

By C. F. Ellis

Interest in the composition of automobile exhaust gases has been greatly accelerated by recent studies that have indicated that these gases contribute to smog formation in urban areas. Several analytical methods have been published for the analysis of the hydrocarbons in the exhaust gases, but similar information has not been published on the analysis of the oxygenated compounds. This report presents procedures for chemical analyses of certain oxygenated compounds, procedures for sampling the exhaust gases for these analyses, and the analytical results of some experimental work in which these procedures were used. A stationary 1956 model, 170 horsepower, V-8, dynamometer-mounted engine, operated to simulate vehicular cruise conditions, was used for the study. Exhaust gases produced from a regular-grade Midcontinent gasoline during 15-40- , and 60-mile-per-hour cruise operations were analyzed by chemical methods for formaldehyde, total aldehydes, total carbonyls, total alcohols, carbon associated with the oxygenated compounds, and the oxides of nitrogen. Experimental results indicate: 1. The range of concentrations of the total of the functional groups of oxygenated compounds, expressed as moles per million moles of water-free exhaust gases, is about 90-100; the concentrations increase with engine speed. 2. Aldehydes comprise about 80-90 mole- percent of the total of the oxygenated groups, and formaldehyde accounts for about 50 mole-percent of the total aldehydes. 3. The order of magnitude of the concentration of the carbonyls is the same as that for the aldehydes, indicating that ketones are not a major group. A colorimetric test indicates that methyl ketones Constitute about 2 mole-percent of the oxygenated compounds.

Jan 1, 1961

By Lowell Stroud

Since 1929, the Helium Activity of the Bureau of Mines has operated a helium-extraction plant at Amarillo, Tex. The natural gas that supplies this plant is obtained from the Cliffside geologic structure 12 miles to the northwest and over the years, has become known simply as "Cliffside gas," There is need for published data on the low-temperature phase equilibria of helium-bearing natural gases. To date, little information has been published on the equilibrium phase compositions, solution of helium in condensed natural gas, condensation characteristics, or equilibrium vaporization coefficients for methane, nitrogen, and helium in helium-containing systems. A windowed phase equilibrium apparatus (8)6 was used to obtain 105 equilibrium samples, representing 35 experimental conditions of condensed Cliffside gas at pressures of 100, 200, 300, 400, and 500 p.s.i.a. and temperatures from 0° to -270° F. Data on equilibrium vapor-liquid composition for Cliffside gas are presented in both tabular and graphic form and are discussed in detail to show their relationship to certain criteria that must be met to effect an efficient separation of helium from natural gas by means of low-temperature processes. Facts about condensation characteristics and solution of helium in the liquid phases are included, The important relationship of these two factors in decreasing the percentage of total helium lost by solution in the liquid phase is discussed.

Jan 1, 1961

By R. Barany

Thermodynamic calculations pertaining to the minerals gibbsite, kaolinite, halloysite, and dickite have been hampered by the lack of adequate heat and free energy of formation data. Previous data for gibbsite were highly uncertain, and there were no data for the other three substances. By use of hydrofluoric acid solution calorimetry, the Bureau of Mines derived heat of formation values from the elements and from the oxides for the four substances, and the data were combined with known entropy values to obtain the corresponding free energies of formation. The results show that gibbsite and halloysite are thermodynamically unstable with respect to the oxides (a- alumina, a- quartz, and liquid water) at 298.15° K,, while kaolinite and dickite are only moderately stable (to about the same degree), The instability of halloysite, in comparison with kaolinite and dickite, results in a 60°-lower equilibrium decomposition temperature.

Jan 1, 1961

By M. H. Stanczyk

Bench-scale laboratory tests were made by the Bureau of Mines of a segregation-flotation concentrate, assaying 20.43 percent copper, to investigate the influence of various ratios and concentrations of ammonia and carbon dioxide on copper extraction. Leaching the concentrate with a solution containing 900 pounds of ammonia and 360 pounds of carbon dioxide per ton of feed, followed by washing the leach residue with 1.75 tons of a 10-percent solution of ammonium carbonate and about 1 ton of water (as steam) per ton of solids, resulted in a copper recovery of 96.3 percent. Resegregation and flotation tests of the washed residues revealed that 85 percent of the copper in the residue could be recovered. Steam distillation tests of a typical ammoniacal leach liquor, assaying 39 grams copper, 105 grams ammonia, and 77 grams carbon dioxide per liter, recovered over 99 percent of the copper as a mixed oxide-carbonate precipitate. The ammonia losses in leaching, filtering, washing, and distillation were 0.12 pound per pound of copper recovered in the precipitate. Calcination and subsequent hydrogen reduction of the precipitate yielded a metallic copper powder assaying 98 percent Cu, 0.87 percent Si02, 0.10 percent MgO, 0.54 percent CaO, and 0.41 percent R203.

Jan 1, 1961

By P. M. Sullivan

The principles and application of amalgam electrolysis to the recovery of zinc and tin from secondary products were studied; this Bureau of Mines project was one phase of investigating the development of more efficient methods for processing iron-bearing zinc and tin to produce both base metals of high purity. Zinc of 99-99-percent purity was recovered from galvanizer's dross with recovery efficiency of 98 percent. Tin of 99.9-to 99.99-percent purity was recovered from hardhead with recovery efficiency of 81 percent. Both materials were treated by the same method in separate systems. Mercury was used to leach zinc from dross and tin from hardhead to form amalgams of each metal, both of which were subsequently refined electrolytically to produce high-purity metal. Impurities that were contained in both secondary products behaved as theoretically predicted; impurities that were insoluble in mercury remained as sludge in the leaching column. Except for lead, the readily amalgamated impurities were prevented from fouling the electrolyte by the blocking action of the amalgam electrode. Lead impurity in the tin-refining system dissolved and immediately precipitated as the sulfate. The primary advantage of the amalgam refining method lies in direct recovery of the extremely pure base metal from highly contaminated secondary material.

Jan 1, 1961

By P. C. Good

Tungsten metal in fused form and of high purity was prepared by reducing tungstic oxide with redistilled calcium metal in a heavy-walled sealed reactor. Alloys of tungsten with vanadium, molybdenum) chromium, columbium, and tantalum were prepared by coreduction of mixed metal oxides in the same manner. This work was undertaken by the Bureau of Mines to investigate new approaches for preparing tungsten and its alloys in high-purity form. The standard method of producing tungsten metal has been the reduction of tungstic oxides by hydrogen. The resulting metal powder is compacted, sintered, and fabricated by powder metallurgy methods. Long experience in this field has resulted in the development of a technology that (by careful control of the variables such as metal composition, particle size, and sinterng technique) is well adapted to producing wire and the small shapes usually prepared from tungsten metal.

Jan 1, 1961

By John P. Capp

The feasibility of simultaneously burning several paths through a coalbed to develop a multiple path underground gasification system was investigated by the Bureau of Mines during two experiments, Boreholes were drilled through the overburden and into the coal and arranged in a circle approximately 50 feet from a central borehole. In the first experiment, in an area which had previously been hydraulically fractured,5 air was injected at the center borehole. The coal was ignited at the other boreholes and the fire fronts traveled toward the center, counter to the flow of air, to backward burn paths through the coalbed. Two paths were linked during the first 5 days of operation. The outlets of these two paths were throttled and air pressure was increased to maintain the flow of air, but no other linkages were made. Fourteen days after the two linkages these two paths were opened and gasification was carried on for 10 days, but with only moderate success. In an effort to overcome operating difficulties air was injected at the peripheral boreholes, and the gases were drawn off at the center borehole. Reversed flow operations continued for 12 days and two more paths linked. The heating value of the gas generally was higher than 100 British thermal units per standard cubic foot (B.t.u. per std. c.f.). Because only four of seven paths linked, however, the entire system could not be evaluated with respect to product-gas output and recovery of energy.

Jan 1, 1961

By E. R. Palowitch

This report stems from a study by the Bureau of Mines of the possibility of reducing coal filter-cake moisture by applying radiant heat directly to the filter cake while under vacuum during the drying phase of the filter cycle. One disk of a 4-foot-diameter vacuum filter was equipped with gas-fired radiant-heat generators and the effect of radiant heating on the moisture content of a variety of filter cakes was studied. The results of this investigation show that this process can best be described as a filter aid capable of increasing the effectiveness of conventional filtration approximately 6 percentage points of moisture. The operating cost of removing water by this method is somewhat lower than the average operating cost of thermal drying and is considerably cheaper when the total cost is considered. Removal of water from coal that has been wet-cleaned is an important part of the overall coal preparation process. Water is a contaminant, and it is foolish to wash coal to reduce its ash content and add inert water in the process. In some instances the removal of water is actually more important than the removal of ash-forming minerals; its weight adds to the cost of transportation, and its evaporation during burning or carbonizing absorbs useful heat. Fine coal that contains more than about 10 percent moisture is notoriously difficult to handle. A problem thus exists for which there are sound practical and economic reasons to seek a solution.

Jan 1, 1961

By Donald F. Smith

This report describes the construction and calibration of two ice calorimeters and includes results of high-temperature heat-content measurements, made by the Federal Bureau of Mines, on rubidium fluoride, hafnium tetrafluoride, cesium chloride, and cesium iodide. The heats and entropies of fusion of rubidium fluoride, cesium chloride, and cesium iodide have been calculated at their respective melting points using equations derived from the experimental heat-content data. Hafnium tetrafluoride did not melt within the range of temperatures investigated. Heat and entropy of transition of cesium chloride from the alpha to the beta form were also determined. INTRODUCTION Free-energy data usually afford the cheapest and quickest means of determining the feasibility of experimentally untested reactions. For known reactions, free-energy data show the variation of the equilibrium constant with temperature and make it possible to calculate, without experiment, the maximum ratio of product to raw material for a given chemical process.

Jan 1, 1961

By M. E. Tyrrell

Despits its high melting point (2,135° C.), resistance to attack by molten metals, and its hardness (8), spinel (MgO?Al203) synthesized by the fusion of alumina (Al 2 0.) and magnesia (MgO) is not used on a large scale as a commercial furnace lining, mainly because of the prohibitive cost. This investigation by the Federal Bureau of Mines was prompted by the possibility of producing synthetic spinel from inexpensive raw materials by methods outlined in U.S. Patent 2,029,773, "Process for Obtaining Products Containing Spinets," dated February 4, 1936. In this patent Ture B. Haglund described a process for recovering crystalline spinels from melts in the system Mg0?Al203-2CaO-SiO2, a system well suited to the use of starting materials such as dolomite CaMg(C03)2, olivine [2(Mg?Fe)0.Si02], and bauxite (Al203?2H20) which are abundant in the southeastern United States. Compositions, ranging from a low content in the eutectic mixture of 35 percent spinal and 65 percent dicalcium silicate (2 CaO?SiO2) to a high of 75 percent spinel and 25 percent dicalcium silicate, were fused in electric furnaces of the arc-resistance and internal-resistance types. So long as members of the system were in proper chemical balance, "dusting" slags could be produced over the entire range of spinel concentration.

Jan 1, 1961

By Scott W. Hazen

In recent years many mining companies have recognized that their chance for continued economic survival depends on the adaptation of technological advances in their operations. Increased productivity through new developments in mining methods and improvements in equipment has made mining and processing of lower grade ores possible. Cost analysis has produced accurate data on the costs for development, production, and processing of ore. All of these changes and cost studies have shown the necessity for increased accuracy in determining the grade of ore. Methods of estimating grade in a mineral deposit have not kept pace with the technological advances in the other areas. The same methods are in use today as in the past. Experience and judgment are major criteria of accuracy and the results are highly subjective. In 1953, as part of its research program to develop a better understanding of fundamentals of mining technology, the Federal Bureau of Mines began a sampling method research project at its Denver Mining Research Center. The basic objective of the project is to investigate sampling methods and to study the adaptation of the techniques of statistical analysis to mine sampling.

Jan 1, 1961

By W. L. Schmidt

The effect of a water-repellent film in sandstone cores on the effective permeability-saturation relationship was investigated as part of a cooperative research program between the Bureau of Mines and the American Gas Association. The repellent film was formed by the reaction of methyltrichlorosilane3 with the connate water in the core. Other researchers have reported on the use of silicone chemicals to alter the flow characteristics of porous media (1-3, 5-7, 9, 10).4 The previous studies, however, dealt almost entirely with oil-water or oil-gas systems and not with water-gas systems. The primary purpose of this study was to determine the feasibility of using silane to retard the influx of water into natural-gas storage wells and to determine the necessary requirements for achieving this result. The success or failure of silane treatment as a remedial measure depends on its effect on gas-production rate and attendant water production.

Jan 1, 1961

By Charles W. Huggins

Electron diffraction and electron microscopy were used to determine the unit cell parameters of garnierite [(Ni,Mg)3 Si2O5 (OH)4] and to examine its crystal habit. Bundles of ribbons, many less than 200 A. in cross section, make up the bulk specimen of the garnierite Electron diffraction revealed the unit cell to be monoclinic. Unit cell parameters were: a, 5.33 A,; b, 9.23 A.; c, 14.96 A.; and ß, 94°441.

Jan 1, 1961

By R. F. Stewart

A sedimentation method involving the use of the Palo-Travis apparatus was found satisfactory for rapid determination of the size distribution of coal particles ranging from 10 microns in diameter to those passing an 840-micron opening (20-mesh sieve), The method is most useful for comparing the size distributions of samples of pulverized coal where the actual size of the particles is not required and is applicable to sieve and subsieve sizes of a wide variety of coals and chars that can be wetted and are heavier than water. An analysis, including all calculations, can be completed in 1/2 to 10 hours, depending on the time required for the finely divided coal to settle. A typical analysis requires about an hour, making this a rapid, precise method for routine size-distribution analysis of powdered coals. When used with coal particles smaller than 400 microns, the method is precise within 15 microns for wide variations in test conditions and within 5 microns for identical test conditions. The precision decreases as particle size increases, becoming unsatisfactory for particles larger than 400 microns (40-mesh). For precision within 15 microns, the samples must be equal in weight. Greater precision is obtained with 4-gram samples, but samples as small as l gram may be used.

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 K. K. Kershner

Nickel having a purity of more than 99.99 percent with reference to metallic impurities was electrodeposited at the Rolla Metallurgy Research Center of the Federal Bureau of Mines. The production of high-purity nickel is in keeping with the current trend in technologies for producing metals with lower and lower percentages of impurities. To understand more fully the role to be played by nickel by itself and as a component in many alloys, the element must be in a state of high purity. Procedures are outlined for purifying nickel solutions by precipitating and filtering off impurities. Details are given for using the purified solutions as electrolytes in depositing high-purity nickel. The elecneleposited nickel contained 0.0005 to 0.002 percent each of cobalt, copper, aid iron together with spectrographically detectable traces of aluminum, magnesium, and silicon. The deposits were smooth and dense; the crystalline structure was typical of an electrodeposited metal. Some preliminary experiments for purifying nickel solutions by liquid-liquid extraction are also described in this report. Tests of this type were limited since more encouraging results were obtained by other methods of purification.

Jan 1, 1961

By D. Bienstock

A high-B.t.u, gas can be synthesized by the catalytic methanation of a mixture of 2.5 to 3 parts of hydrogen to 1 part of carbon monoxide, obtained in the gasification of coal, using a steel catalyst followed by Raney nickel in a hot-gas-recycle system. Conversion of 99 percent of the H2+CO yields a fuel gas with a heating value of 983 to 1130 B.t.u. per cubic foot containing 78 to 96 percent methane, no carbon monoxide, and very small amounts of unsaturated hydrocarbons. With the steel catalyst alone, conversions were 85 to 90 percent, giving a fuel gas of 810 to 868 B.t.u, per cubic foot, or 847 to 975 B.t.u. on a C02-free basis. INTRODUCTION In 1948 the U.S, marketed production of natural gas was 5.15 trillion cubic feet; by 1958 it had reached 11.0 trillion cubic feet, a rate of growth of 8 percent annually. 4 5 Although demand is expected to increase less rapidly, by 1966 it may reach 16 trillion cubic feet, based on an estimated 4.7 percent annual increase.6

Jan 1, 1961