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By R. H. Nafziger

The Bureau of Mines evaluated 18 domestic titaniferous materials with widely varying compositions, mineralogy, and physical properties in electric-arc furnaces, Techniques were devised to recover both the titanium and iron values contained in these materials so that the reliance of the United States on foreign sources of higher grade ilmenites and rutile might be decreased. Most of the tested titaniferous materials responded well to lower grade or byproduct reductants, such as bituminous coals, charcoal, and coke breeze. Sufficient slag fluidity was realized by maintaining from 8 to 12 wt-pct iron in the slags; no contaminating fluidizers were required. Fluid slags containing up to 79, 70, and 54 wt-pct Ti02 were realized from east coast ilmenites, a rock ilmenite, and a titaniferous magnetite ore, respectively. A carbon-lined furnace shell is recommended for minimum slag contamination. Good results also were obtained during extended submerged-arc furnace tests.

Jan 1, 1980

By Steven J. Page

Responding to the increasing concern for dust control in metal and nonmetal mining, the Bureau of Mines investigated typical dust reduction efficiencies of wet bar cutter machines as they are presently being used in salt mines. Wet bar techniques have previously been used in coal mines, achieving dust reduction efficiencies ranging from 11 to 60 pct. Two different wet bar techniques, namely, the front spray and the water trickle, have been studied as they are currently being used in two salt mines. Preliminary results show that the dust reduction efficiencies have a large variation (0 to 66 pct), as is the case for wet bars used in coal. However, whereas wet bars in coal required 3 to 4 gpm water consumption, wet bars in salt obtained similar efficiencies with only 0.1 to 0.4 gpm. The most reliable data obtained during this study show that the front spray system consistently performs at efficiencies between 41 and 66 pct, with an average of 54 pct. The results indicate that, although wet bar cutter techniques in salt mines are a relatively simple and inexpensive means of dust control with a minimum of water consumption, further investigation should be performed to fully evaluate and optimize wet bar cutter dust reduction efficiencies.

Jan 1, 1980

By Nicholas Kyriazi

It is of interest to know how to obtain as high an absorption efficiency as possible from a CO2-absorption canister used in closed-circuit breathing apparatus. In this study the Bureau of Mines found that varying the bed depth and the cross-sectional area of a canister changes its absorption characteristics. In tests using four ,1 rectangular, variable-depth canisters with different cross-sectional areas, the Bureau found that, given a constant weight of the chemical absorbent, LiOH, and a constant COa input, the canisters with a greater cross-sectional area reached C02 levels of 0.5 volume-percent in the effluent gas sooner than did the canisters with a greater bed depth. However, resistance to flow through the canister increases with bed depth, and a trade-off is inevitable. It was anticipated that the efficiency of a canister would increase with increasing intergranular air space approaching the tidal volume of the breathing waveform and then level off at some point under 100 percent. This postulation was partially substantiated. Cylindrical and radial canisters were also tested and compared. It appears that shape is not as important a factor in absorption efficiency as bed depth, since neither canister differed significantly from the rectangular canisters with regard to absorption efficiency values.

Jan 1, 1980

By J. E. Pahlman

As part of its effort to reduce the need for strategic minerals through conservation and to reduce the capital and energy requirements of mineral processing, the Bureau of Mines has investigated a method for preparing ferrochromium alloys containing less than 2 percent carbon. This method will conserve chromium and should reduce the capital and energy requirements for chromite reduction. Reduced products containing less than 2 wt-pct C and as low as 0.01 wt-pct C were obtained by reacting pellets of chromite and carbonaceous reductant mixtures at pressures of 0.1 to 1 torr and temperatures of 1,230° to 1,320° C. The extent of reduction increased with increased temperature and decreased pressure; however, operating conditions were limited due to the onset of significant chromium vaporization at higher temperatures and lower pressures. Foundry coke, anthracite, and carbon black were found to be supe¬rior to graphite as reductants. The reduction of chromite to metallics was found to proceed via the carbide intermediates (Fe,Cr)7C3 and (Fe,Cr)23C6, No evidence of carbide intermediates Fe3C or Cr3C2 was found. Buttons of ferrochrome alloys were made by melting a mixture of reduced products with CaO and Si02 at 1,700° C for 20 minutes in an induction furnace,

Jan 1, 1980

By W. P. Diamond, J. R. Levine

The explosion hazard of methane-air mixtures has become an increasingly serious mine planning problem, and an advance assessment of methane gas potential can therefore be essential for a safe and economic mine development pro- gram. As part of its coal mine health and safety program, the Bureau of Mines has developed a simple, inexpensive test to measure the methane content of coal samples obtained from exploration cores. The gas content of coal per unit weight as determined by the direct method test can be used as a basis for a preliminary estimate of mine ventilation requirements, and to determine if degasification of the coalbed in advance of mining should be considered. Since the Bureau began measuring the gas content of coal samples in 1972, experience has led to equipment and procedural changes, the most significant of which has been the development of a ball mill for crushing the coal sample to release the residual gas at the end of the desorption test period. This revised procedure replaces the crushing box and graphical methods described in earlier Bureau publications. The results of 583 direct method tests are summarized in tabular form. These results include data on the gas content of 125 coalbeds in 15 States.

Jan 1, 1980

By W. P. Diamond

The explosion hazard of methane-air mixtures has become an increasingly serious mine planning problem, and an advance assessment of methane gas potential can therefore be essential for a safe and economic mine development program. As part of its coal mine health and safety program, the Bureau of Mines has developed a simple, inexpensive test to measure the methane content of coal samples obtained from exploration cores. The gas content of coal per unit weight as determined by the direct method test can be used as a basis for a preliminary estimate of mine ventilation requirements, and to determine if degasification of the coalbed in advance of mining should be considered. Since the Bureau began measuring the gas content of coal samples in 1972, experience has led to equipment and procedural changes, the most significant of which has been the development of a ball mill for crushing the coal sample to release the residual gas at the end of the desorption test period. This revised procedure replaces the crushing box and graphical methods described in earlier Bureau publications. The results of 583 direct method tests are summarized in tabular form. These results include data on the gas content of 125 coalbeds in 15 States.

Jan 1, 1980

By S. E. Khalafalla

In support of its goal to maintain an adequate supply of minerals to meet national economic and strategic needs, the Bureau of Mines has investigated a novel hydrometallurgical system with sulfur dioxide. Differential leaching with dissolved SO2 of manganese, nickel, and cobalt from their hydrous oxides was found to be very rapid and efficient--almost instantaneous and quantitative. In this method a given weight of mixed oxides previously ground to minus 200-mesh is slurried with a leach solution containing a specified quantity of dissolved SO2 for 10 minutes at room temperature and ambient pressure. An empirical leaching parameter, R, is defined as the ratio of the number of SO2 moles in the leaching solution to the weight of the metal oxide charge. Plots of the variation of metal extraction with the ratio R generate a series of sigmoidal-shaped curves, each of which is characteristic of a specific metal extraction. A threshold value of R is required to initiate the leaching of a given metal from the mixed oxides. Once this threshold is reached, the metal recovery can increase to more than 95 pct in very short times. For increasing values of R, the extractability of various metals by SO2 follows the order: Mn > Ni > Co >> Fe, Al, Cu. Differences in the threshold R values permit a variety of metal separations to be made simply by adjusting the quantity of SO2 in the contacting solution. Success in this leaching system depends upon comminuting the sea nodules to less than 0.149 mm (100-mesh). Above this critical size, leaching is slowed due to the inaccessibility of inner particle reacting groups to the SO2 leaching agent. This results in nonselective extraction and less extraction of preferred metal values. At or below 0.149 mm, leaching by SO, is possible with all its attributes of selectivity, sensitivity, and rapidity. Leaching with HC1 solutions of the same pH level as dissolved SO2 yielded mixed, slow, and incomplete metal extractions. This observation rules out any interpretation based on hydrogen ion as the leaching agent. The leaching curves resemble the complexometric titration curves of heavy metals with specific coordination species.

Jan 1, 1981

The Bureau of Mines conducted large-scale laboratory copper ore leaching tests to enable improving copper recovery from large dump-leaching operations. This was done by comparing leaching progress when copper was recovered from recycled leach liquor either by cementation or by solvent extraction. Copper was leached from 7-ton ore samples at room temperature using pH 2 ferric sulfate solutions. With are samples containing 11 percent minus 0.5-inch fines, no marked advantage in using either of the copper recovery methods was evident after 416 days of leaching. With ore containing 32 percent minus 0.5-inch fines, solvent extraction of copper was advantageous in that 60 percent of the copper was extracted after 568 days, whereas only 48 percent of the copper was extracted when cementation was used. Less acid was consumed during leaching when solvent extraction, rather than cementation, was used for copper recovery. Iron, contributed by cementation with scrap iron, plugged the ore bed containing 32 percent fines.

Jan 1, 1981

By M. J. Sapko

A moderately scaled apparatus was developed by the Bureau of Mines to determine the fire resistance characteristics of mine conveyor belts and similar type materials. The design of the apparatus was based upon data obtained in full-scale fire tests and features a radiant panel to preheat the belt and a methane-oxygen ribbon burner to ignite the sample under ventilating condi¬tions in a rectangular duct. The test method overcomes the limitations of existing laboratory-scale methods and provides a measure of both ignitability and flammability in quantitative terms. Flame propagation depended upon such variables as air velocity, ignitor heat flux, and belt width and height in the test chamber. Data are presented for nine belt materials and fire resistance ratings are proposed in terms of the flame spread rate, heat release rate, and the critical ignitor heat flux. The ratings discriminate between the fire hazard posed by different fire-resistant belts and tend to be in reasonable agreement with those obtained in full-scale fire tests.

Jan 1, 1981

By L. A. Haas

The Bureau of Mines conducted bench-scale leaching tests with recycled spent copper electrolytes and copper-nickel mattes produced from the Minnesota Duluth Complex concentrates. This report describes the first stage of an overall two-stage leach operation. The objective of this research was to determine the matte-leach technology required to convert spent copper electrolyte into an enriched nickel liquor suitable for a nickel refinery and there-fore essentially free of copper, iron, and sulfuric acid. The experimental variables investigated were matte composition, particle size, spent electrolyte content, pulp concentration, oxygenation, temperature, and time. The time required to produce an enriched purified nickel liquor decreased with increasing pulp concentration, temperature, and oxygenation, but increased with increasing particle size and electrolyte copper and acid content. Nickel-rich (about 50 g/l) liquors at a pH of about 4 and containing less than 1 g/l of copper and iron were produced at 70° C by leaching minus 325-mesh low-iron (less than 5 pct) matte for 8 hours with spent electrolyte containing 22.4 g/l Cu, 28.9 g/l Ni, less than 0.1 g/l Fe, and 50 g/l H2S04 at a pulp concentration of 1 kg of matte per liter of spent electrolyteo Varying the nickel content of the spent electrolyte from 11 to 101 g/l appeared to have no appreciable influence on the matte leaching characteristics.

Jan 1, 1981

By C. F. Davidson

The Bureau of Mines studied the extraction of lithium from lithium-containing clays by chlorination with hydrogen chloride (HC1). In bench-scale laboratory investigations, HC1-H20 mixtures were used to selectively chlorinate lithium, but not calcium or magnesium, in lithium-containing clays. The addition of calcium carbonate to the clay was found to improve the lithium recovery. Reaction conditions found to affect the lithium recovery were ratio of clay to carbonate, reaction temperature, and HC1 concentration. The best conditions for selective chlorination of the lithium were 2:1 clay-carbonate, 750° C, and 20 wt-pct HC1. The experimental results and trends in lithium extraction are explained using thermodynamic relationships.

Jan 1, 1981

By M. J. Ferrante

High-temperature enthalpy and X-ray powder diffraction studies were con-ducted on aluminum sulfide (Al2S3) as part of the Bureau of Mines effort to provide new data for the advancement of mineral technology consistent with environmental preservation and energy conservation. Relative enthalpies were measured with a copper-block calorimeter from 298.15 to 879 K. Tabulated values are listed for heat capacity, entropy, Gibbs energy functions, and relative enthalpies between 298.15 and 900 K. Enthalpies were also given in the form of an equation and combined with published data to calculate standard enthalpies of formation and Gibbs energies of formation for reactions of crystalline aluminum with crystalline, liquid, and gaseous diatomic sulfur. The hexagonal, rhombohedral, and cubic phases of Al2S3 were identified by X-ray powder diffraction studies, and the indexed powder diffraction patterns of these phases are given. The hexagonal phase was stable to about 852 K and was partially converted to the rhombohedral form at 879 K.

Jan 1, 1981

By V. R. Spironello

The Bureau of Mines is conducting studies of the slags related to ferrous technology to evaluate acceptable substitutes for the auxiliary flux, mineral fluorspar, in foundry operations. This work is directed toward the Bureau's goal of minimizing the Nation's dependence on scarce and critical minerals Comparative basic practice cupola (18-inch-ID) trials were made to evaluate a waste material called "used potlining," which contains significant levels of fluorine, sodium, and aluminum in various compounds. Used potlining is recovered from alumina reduction cells after its useful life, and was supplied by the Aluminum Co. of America (Alcoa) to the Bureau for evaluation. The material in the lump and pelletized form (with limestone) provided extremely fluid slags based on visual observation during cupola operation. No adverse effects were found on cupola performance, metal and slag chemistry, the environment, or mechanical properties of the castings produced. Fluorine recovery in the slag was equal to, or higher than, that of fluorspar; fluorine losses to the scrubber water and solids were lower. The acidity of the scrubber Hater was somewhat neutralized. No difference was observed in furnace-refractory attack, as determined by the level of magnesia in the slag and visual inspection. The recovery of sodium in the slag, presumably as the oxide, significantly increased slag fluidity, suggesting that less than equivalent fluorine may be required. There was no contamination of the gray iron by the aluminum from the used potlining. Used potlining was completely satisfactory as a substitute for fluorspar in cupola ironmelting.

Jan 1, 1981

By E. R. Cole

This Bureau of Mines investigation was prompted by the need forr a stable anode for electrowinning metals, particularly zinc and copper, from acid solutions. The polarization behavior of Pb-Ag (1 pct Ag) anodes in H2SO4 and fluoride solutions was determined as the first step in the development of such an anode. A Luggin capillary, dc power supply, high-impedance voltmeter, and other equipment standard to an electrochemical laboratory were used in this study. It was determined that during polarization, a relatively hard, stable coating of Pb02 was formed on the surface of the lead-silver anode and the rate of formation of this coating was considerably enhanced by the presence of fluoride ions in solution. Subsequent investigations at the Bureau of Mines Rolla Research Center resulted in the development of a Pb02-coated titanium (Pb02-Ti) anode. Results of this effort were presented in Bureau of Mines Report of Investigations 8111. Additional data resulting from extensive testing of the Pb02-Ti anodes, as well as process improvements and innovations, are included in this report. The anodes were considered generally unsatisfactory for zinc electrowinning because of lower conductivity, higher oxygen overvoltages, and shorter in-cell life as compared with the Pb-Ag anodes now being used in industry. However, the PbO2-Ti anodes were used successfully to oxidize waste chromium solutions and to electrowin copper.

Jan 1, 1981

By Philip C. Good

The Bureau of Mines investigated the feasibility of utilizing low-grade phosphatic shale as a feed for phosphoric acid production. Present practice in the phosphate mining operations of southeastern Idaho is to remove and either stockpile or waste low-grade phosphatic shales as the high-grade phosphate beds are selectively mined. Acid digestion studies were performed on uncalcined shale and on shale calcined to remove free carbon to determine phosphoric acid quality, yield, and amenability to filtration. The untreated shale, containing 21.4 pct P205, was digested with sulfuric acid in a single-tank reactor to yield phosporic acid and gypsum residue. Although 96 pct P205 recovery was attained in digesting uncalcined shale, only the calcined product gave satisfactory filtration rates. Calcined shale yielded phosphoric acid recovery of about 93 pct of the contained P205. It was higher in impurities than commercially prepared acid derived from high-grade western phosphate rock. An acid filtration rate of 745 lb P205/ft2/day was attained. This value is lower than the rate of 900 lb P205/ft that is generally considered to be acceptable in industrial production of phosphoric acid from high-grade phosphate rock.

Jan 1, 1981

By W. N. Marchant

The Bureau of Mines performed chemical research to elaborate details of sulfur chemistry pertaining to the citrate flue gas desulfurization process in which sulfur dioxide (SO2), absorbed (as bisulfite ion) in a buffered sodium citrate solution, is reduced by hydrogen sulfide (H2S) according to the overall reaction 2H2S + HSO3 + H+ ? 3S + 3H20. The rate-limiting step in the process was shown to be the reduction by H2S of thiosulfate (S2031-) that is formed as an intermediate. Pseudo first-order kinetic measurements were made at room temperature to retard the reaction sufficiently that adequate analysis was possible. These measurements showed the rates of the following net processes to be -d [S02]/dt (pH 4.5) = (0.409±0.050)min-1 [S02]; d [S2032-]/dt (pH 4.5) = (0.199±0.017)min-1 [S02]; -d [S2032-]/dt (pH 4.0) = (0.0437±0.0265)min-1 [S2032-]~1; -dH2S/dt (pH 3.9) = (21.6±3.0) mmoles/min-atm [H2S]g1.4, where [H2S]g is the partial pressure of H2S in the gas phase, in atmospheres, and the rate describes the consumption of H2S, in millimoles per minute; d[S]/dt (pH 4.0) = (38.0±3.4)min-1 [H2S]1, where [H2S] is the concentration of H2S in solution. Hydrogen ion consumption during the slow phase of regeneration was shown to occur at (2.1±0.5) times he rate of thiosulfate consumption, which is interpreted as evidence for the following as the rate-limiting reaction: 2H2S + S2032- + 2H+ ? 4S + 3H20 A scheme consisting of five sequential general reactions is proposed to account for sulfur formation.

Jan 1, 1981

By E. D. Calvert

The Bureau of Mines, in its effort to promote greater utilization of domestically abundant materials, conducted reasearch on an alternate mold material that has commercial potential for titanium investment casting. Using variations of the conventional lost wax molding process, investment shell molds were formed entirely of fused, calcia-stabilized Zr02 and a Zr02-forming binder. Optimization of binder/slurry properties', stucco grain size and dis¬tribution, and curing practices resulted in a structurally sound investment shell that was distortion free and thermally stable. Small titanium castings, weighing up to 10 pounds, were prepared in unheated molds by both static and centrifugal casting techniques. Microstruc¬tural examination of the castings revealed that mold fill and surface quality were enhanced by centrifugal casting, although good results also were obtained from the statically poured molds. Microstructural and electron microprobe examinations showed that excessive, brittle case formation could be avoided by curing the dried shell molds in air for at least 2 hours at 1,400° C. Increasing curing temperature and time above these levels yielded added bene¬fits. Molds fired in vacuum at 1,500° C for 4 hours yielded castings essen¬tially free of case formation. The tensile properties of as-cast test specimens (no surface conditioning performed) id the chemical composition of representative metal samples showed that castings produced were comparable to Grades C-1 and C-2 unalloyed titanium This indicated that no sifnificant degradation of metal properties resulted from mold/metal interaction.

Jan 1, 1981

By Kenneth L. Cashdollar

This report describes three types of optical dust probes that have been designed, built, and tested by the Bureau of Mines. Each of the probes measures dust cloud concentrations by the attentuation of light. The first is a single-path-length probe, the second is a double-path-length probe, and the third is a single-path-length probe that employs jets of air to keep the windows of the light source and detector free from dust coating. The theory of operation and the calibration procedures for each of the probes are described. The results of the Bureaus laboratory, mine, and field tests of the probes are also reported.

Jan 1, 1981

By Arne Landsberg

The Bureau of Mines has undertaken research to elucidate the chemistry involved in the efficient recovery and control of minor elements in base metal smelting operations. These elements should be effectively recovered not only because they have commercial value, but also because of their potential hazard to workers' health and the environment, if they are not controlled during processing. Cadmium, a minor metal in zinc ores, is the subject of this report. The roasting step of the complex zinc-smelting process was chosen for investigation because of the high potential for removing cadmium by volatilization during this primary stage. Commercial roaster feed materials were used to determine the sequence of reactions and the effect of these reactions on the volatilization of cadmium. Electron microprobe examination of both the commercial roaster product and oxidized sulfide solid solutions prepared in the laboratory showed that oxidized iron was of prime importance in preventing cadmium volatilization. The mechanism by which iron prevents cadmium volatilization is proposed, and a preheating technique is recommended for more effectively recovering cadmium prior to roasting.

Jan 1, 1981

By R. A. Bloomfield

This report summarizes Bureau of Mines contract research on the disposal of retorted oil shale. A data base has been developed describing the physical-chemical properties, geotechnical engineering properties, and natural cementation characteristics of spent shale. Results of field compaction tests and seepage pond tests are presented, along with results of a partially saturated finite element seepage model used to predict infiltration and seepage rates. Preliminary engineering analyses are presented for underground disposal systems, which include material transport methods, and for a surface disposal system, which includes stability analyses.

Jan 1, 1981