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By L. J. E. Hofer

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

Jan 1, 1963

By G. W. Birge

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

Jan 1, 1963

By W. W. Weller

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

Jan 1, 1963

By P. E. Churchward

Rhenium sources and recovery methods were investigated by the Bureau of Mines to delineate potential resources of the metal. The only significant rhenium resource appears to be about 28,000 lb of rhenium contained in the domestic annual output of approximately 20,000 tons of byproduct molybdenite concentrates from porphyry copper operations. An estimated 70 to 80 pct of this rhenium is potentially recoverable by processing the rhenium-bearing fumes and dusts obtained during conventional roasting of molybdenite concentrate. At 70 pct recovery this would amount to 19,600 lb of rhenium. A more conservative estimate by the Committee on Refractory Metals of the National Research Council (1513 is that 12,000 lb of rhenium metal could be produced annually from current production of molybdenite from porphyry copper operations in the United States. A procedure was developed in the laboratory for recovering rhenium in the form of electrolytic flake by electrowinning the metal from a solvent extraction strip solution. The procedure included (1) water leaching of molybdenite roaster flue dust, (2) selective extraction of rhenium from the leach liquor by contacting it with a kerosine solution of a quaternary amine, (3) stripping of rhenium from the loaded organic solution by a perchloric acid solution, and (4) electrodeposition of rhenium from the loaded strip liquor. Raw material for the studies was flue dust containing 0.48 pct Re, 35 pct Mo, and 23 pct S in sulfide and sulfate form, and small amounts of numerous metallic impurities. Water leaching dissolved 85 pct of the Re and yielded a solution that was 13 in sulfuric acid and contained, 1 g/l Re and 16 g/l Mo. The solvent extraction strip solution that was electrolyzed for rhenium deposition was 1 molar in perchloric acid and 1 molar in ammonium sulfate and contained 13 g/l Re and 0.01 g/l Mo.

Jan 1, 1963

By L. B. Pankratz

High-temperature heat-content values of pure lutetium sesquioxide and dysprosium sesquioxide were measured over the temperature range from 298° to 1,800° K. Similar data for cerium sesquioxide were calculated from measurements of a mixture of cerium sesquioxide and dioxide and known values for cerium dioxide. The results for lutetium sesquioxide are regular. Dysprosium sesquioxide has a minor thermal anomaly near 1,590° K, the extra heat absorption being 220 cal/mole, Hexagonal cerium sesquioxide undergoes a transformation around 1,050° K, which is only slowly reversible; consequently results were obtained for both the low- and high-temperature varieties. The original heat-content data are reported, and smooth values of heat content and the corresponding entropy increments are tabulated. Equations were derived to represent the heat-content values.

Jan 1, 1963

By Edward W. Parsons

Conventional rock-bolt anchors often fail when installed in weak formations. The purpose of this work was to develop an anchor that would utilize an explosive charge to secure anchorage in any type of rock. Laboratory work to develop a rock-bolt anchored by explosive forming was initiated using rock-bolt models which had a drilled explosive chamber and were composed of various metals. This was followed by the use of several types of seamless tubing which were expanded with a water-coupled explosive capsule. By attaching a length of solid bolt to the anchor tube, a prototype explosive-anchored rock bolt was made. More than 150 laboratory models were expanded during this phase of development, During two field tests in underground mines (A and B) and one in an open- cut mine (C), 87 explosive-anchored bolts, 9 slot-and-wedge bolts, 2 bolts anchored with expanding grout, and 28 expansion-shell bolts consisting of three types of shells were installed and subjected to pull tests. The field tests were run to determine the effects of variables such as the amount and placement of the explosive charge, design changes in the bolt, and the effect on anchorage of different pull-test techniques. The field tests revealed the following: Mine A. The explosive-anchored rock bolt was feasible, but changes were necessary in bolt materials and in some details of bolt design. Mine B. The design and materials of the bolt gave excellent results in hard fractured rock, but no information was obtained concerning variations in the dimensions of the anchor unit or in the explosive charge. Nine C. Varying the explosive charge to produce a beaded surface on the bolt tube and tightening of the anchored bolt before pull-testing were found to increase significantly the anchorage obtained in soft ground.

Jan 1, 1963

By C. J. Thompson

Two sulfur compounds--the 2,2,5-trimethyl- and the 2,2,5,5-tetramethyl derivatives of thiacyclopentane--were identified in Wilmington, Calif., crude oil, using microdesulfurization and gas-liquid chromtography techniques.

Jan 1, 1963

By G. T. Krempasky

This report covers the installation and evaluation of lb reinforced concrete sets, 6 in each of 3 mines in the Goeur d'Alene mining district, Shoshone County, Idaho, and is the second of a series to determine the feasibility of a more permanent type of mine support. Closure measurements, where applicable, were made periodically of the concrete-set installations and were compared to the initial cross section of the sets. A different method of blocking was used at each test site; at one test site the type of blocking was changed several times during the test. Results from each test site are reported separately. No attempt was made to compare the cost of the concrete installations with the cost of other types of support used in the district. Such an evaluation of permanent types of support would require a longer period of time. At this time, tests are not complete enough to determine the applicability of underground concrete supports. However, results to date tend to confirm the general opinion that precast concrete mine supports could be used to advantage in openings that require support and must have long life, especially where decay of timber is an important factor.

Jan 1, 1963

By A. A. Cochran

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

Jan 1, 1963

By M. J. Kovalik

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

Jan 1, 1963

By Charles Prasky

This report describes fluidized bed techniques employed by the Bureau of Mines at Minneapolis to differentially sulfatize the manganese in two samples of low-grade manganiferous ferruginous carbonate slates from the Cuyuna Range district, Minn. Suitable mechanics of operation were established. A space rate of 1.25 to 1.5 fps, a retention time of 3 to 3.5 hours, a temperature of 700° C, and a 10 percent sulfur dioxide gas in air were adequate for sulfatizing the slates by fluidization. Under these conditions the overflow product removal rate from the 4-inch-diameter reactor was 4 to 5 pounds per hour. The sulfur dioxide was used more efficiently in the two-stage treatment than in the single-stage treatment. However, approximately 80 percent of the manganese was converted to sulfate by either treatment.

Jan 1, 1963

By R. E. Mussier

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

Jan 1, 1963

By G. W. Birge

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

Jan 1, 1963

By M. E. Tyrrell

Mixtures of zirconium diboride and iron, cobalt, and nickel were resistance sintered to high-density compacts using modified electric welding equipment. To evaluate the use of iron, cobalt, or nickel as binders for zirconium diboride, the sintered compacts were examined in polished section and tested for crushing strength, hardness, microhardness, oxidation rate, and resistance to mechanical shock. Each of the zirconium diboride-metal mixtures produced brittle cermets, but the hardness was generally satisfactory. The iron- and cobalt-bonded cermets exhibited rather poor oxidation resistance. Cobalt provided the least brittle bond, and nickel, the hardest and most resistant to oxidation. Iron tended to form chalky compacts with low resistance to mechanical shock.

Jan 1, 1963

By J. G. Donaldson

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

Jan 1, 1963

By C. O. Hawk

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

Jan 1, 1963

By David Schlain

A small alumina reduction cell with a graphite crucible and boron nitride liner was developed by the Bureau of Mines as the initial phase of a study of the reactions which occur in the reduction of alumina by the Hall-Heroult process. Operating conditions in the cell such as temperature, time, current density, electrolyte composition, and electrode materials may be varied easily. Aluminum was produced in the cell at a current efficiency of about 75 percent and a cell voltage of 2.7 volts. Although the data are not wholly conclusive, the operation of the cell did not appear to be greatly affected by large changes in temperature, electrode spacing, current density, and alumina concentration in the electrolyte.

Jan 1, 1963

By C. M. McKinney

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

Jan 1, 1963

By Earle S. Burnett

This report outlines the experimental procedures for using a Burnett apparatus to obtain compressibility coefficients for multiphase, multicomponent fluid mixtures. The conventional Burnett method is described briefly whereby multiphase compressibility data can be obtained by first determining the compressibility factor, Z, as an isothermal function of pressure alone. Then starting at conditions of temperature and pressure where Z is known, the fluid is cooled at constant volume to some lower temperature at which the resulting pressure is measured, and a corresponding value of Z is obtained from a fundamental relationship between compressibility factors, pressures, and temperatures at constant volume. The isochoric treatment of the fluid, extended to still lower temperatures and along other isochors, eventually results in compressibility determinations for the whole two-phase system thus covered experimentally.

Jan 1, 1963

By Thomas L. McVay

Laboratory batch and pilot plant flotation tests were made to determine the feasibility of recovering commercial grade kyanite from a quartzite- kyanite rock from the Graves Mountain, Ga., deposit. Best results in laboratory and continuous tests were obtained using sodium carbonate for pH control, citric acid for quartz depression, and oleic acid as the kyanite collector. Over 80 percent of the kyanite was recovered in a concentrate analyzing 56.8 percent Al203 and 3.8 percent hydrochloric acid soluble Fe203. Subsequent treatment of the flotation concentrate by magnetic separation reduced the acid soluble Fe2O3 to 0.6 percent and increased the alumina content to 59.2 percent. Acid leaching of the concentrate gave a product analyzing 59.7 percent Al203 and about 0.1 percent Fe203. As a result of the beneficiation research, a commercial kyanite flotation plant was completed in September 1962 by private industry.

Jan 1, 1963