Search Documents

By Seth C. Schaefer

The Bureau of Mines has determined the standard Gibbs energies (AGf°) of CoS1.035 (cobalt sulfide) and Ni2.515S2 (nickel sulfide) with high-temperature galvanic cells using stabilized Zr02 (zirconia) as the electrolyte. Potential measurements were obtained for the cell Pt, CoS1.035, CoO, S02(g, 1 atm)//Zr02//02(g, 0.0114 atm), Pt, with the overall cell reaction C0S1.035(c) + 1.535 02(g, 0.0114 atm) = CoO(c) + 1.035 S02(g)¬ These results, combined with the best available data for ?Gf° of CoO and S02 from the literature, give the standard Gibbs energy of formation of CoS1.035 for the reaction Co(c) + 0 5175 S2(g) = CoS1.035(c) ?Gf° = -38.890 + 18.87 x 10-3T ± 0.185 kcal/mole (866.0 - 1,104.9 K), where temperature (T) is expressed in kelvins. Similar measurements were obtained for the cell Pt, N12.515S2, NiO, S02(g, 1 atm)//Zr02//02(g, 0.0122 atm), Pt, with the overall cell reaction Ni2.515S2(c) + 3.2575 02(g, 0.0122 atm) = 2.515 NiO(c) + 2 S02(g). Combination of these results with data for ?Gfo of NiO and S02 from the literature yields the standard Gibbs energy of formation of Ni2.515S2 for the reaction 2.515 Ni(c) + S2(g) = Ni2.S1SS2(c) ?Gf° -65.377 + 24.67 x 10-3T ± 0.541 kcal/mole (968.6 -1,053.7 K).

Jan 1, 1981

By Seth C. Scharfer

"As part of the Bureau of Mines effort to provide thermodynamic data for the advancement of mineral technology, the Gibbs energies of formation of MoS2 (molybdenite) and WS2 (tungsten disulfide) were determined with high-temperature galvanic cells employing stabilized Zr02 (zirconia) as the electro¬lyte. In the temperature range from 867 to 1,209 K, potential measurements were obtained for the cellPt, MoS2 , Mo02 , SO2 = 1 atm // Zr02 // 02 = 0.0112 atm, Pt, with the overall cell reactionMoS2(c) + 3 02(g, 0.0112 atm) = Mo02 (c) + 2 S02(g). (1)These results, combined with the best available values for Gibbs energies of formation (?G°f) of Mo02 (molybdenum dioxide) and SO2 (sulfur dioxide) from the literature, give the standard Gibbs energy of formation of MoS2, ?G°f, for the reactionMo(c) + S2(g) = MoS2(c) (2)?G°f = -96.681 + 43.76 x 10-3T±0.538 kcal/mole, (3)where temperature (T) is expressed in Kelvins.Similar measurements in the temperature range from 872 to 1,210 K were obtained for the cellPt, WS2 , W03 , SO2 = 1 atm // Zr02 // 02 = 0.0114 atm, Pt, with the overall cell reactionWS2(c) + 3.5 02(g, 0.0114 atm) = W03 (c)+ 2 S02(g). (4) Combination of these results with the best available data of ?G°f for W03 (tungsten trioxide) and SO2 from the literature gives the Gibbs energy of formation of WS2 in the temperature range from 872 to 1,210 K for the reactionW(c) + S2(g) = WS2 (c)(5)?G°f = -92.429 + 43.88 x 10-3T ± 0.280 kcal/mole. (6)A third-law analysis yields a standard enthalpy (?H°f) for the reaction298Mo(c) + 2 S(rh) = MoS2(c), (7)?H°f = -67.36±0.60 kcal/mole, (8)298where the standard states are pure crystalline MoS2 / and rhombic sulfur."

Jan 1, 1980

By John P. Hager

This study investigated the formation of vapor complexes between aluminum chloride and the chlorides of iron, titanium, and silicon. For the A1-Fe-C1 system the proposed gaseous complex species is Al2Fe2C112(g), which is formed according to the reaction 2A1C13(s) + 2FeCl3(s) = Al2Fe2C112(g) The corresponding free energy expression was determined to be ?G° = 38091.49 - 71.45 ? T 400 < T < 600°K The vapor composition above AlC13 melts contaminated with FeC13 was calculated. In the Al-Ti-CI and Al-Si-Cl systems the proposed vapor complex species are Al2Ti2Cl14(g) and Al2Si2Cl14(g) respectively. Free energy expressions were estimated for the formation of the two complex species. Again, the vapor composition above AlCl3 melts contaiminated with TiCl4 or SiCl4 was determined. The results of this study were compared with previous studies on the three systems.

Jan 1, 1980

By Richard H. Bares

One criterion central to most definitions of reclamation is the restoration of mined lands to their original productive potential. This is often difficult to achieve on mined lands in the Northern Great Plains because of the rigorous climate (Bares 19;2) and various soil related problems including sodicity, salinity, soil permeability, low organic matter and plant nutrient deficiencies (Malakondaiah and Safaya 1982). Field study sites were established on recontotured mined areas during the early 1970&apos;s (prior to the topsoil mandate) in which several amendments were tested for their ability to improve spoil/topsoil conditions and, hence, increase plant production. Physical and chemical properties of these control (untreated) and amended spoils and topsoils have been summarized (Safaya et al. 1982). A number of grass and legume species combinations were studied. The general effects of one time (prior to seeding), single rate (approximately 100 mT ha-1) application of leonardite and/or slack coal to spoils and topsoils was the reduction of grass dry matter yields (NB 1 test site: dry matter yield (DMY) without slack was 110 g m 2 yr I ; DMY with slack was 80 g m -2 yr 1 I and the promotion of legume establishment and yield (SB test site: DMY without leonardite was 13 g m 2 yr -1; DMY with leonardite was 93 g m 2 yr 1). On South Beulah topsoil, treated with leonardite, production of weedy species was remarkably lower than that without leonardite (SB test site: DMY without leonardite was 252 g m - yr -1; DMY with leonardite was 177 g m 2 yr 1). The general effect of commercial fertilizer applied one time prior to seeding (rates ranging from 9-13-0 to 44-1 12-28 kg ha-1 of N-P-K) was to increase plant production during the first two to three years after which the effect disappeared. This effect was much more pronounced on spoils (NB I test site: DMY on spoils without fertilizer was 53 g m -2 yr -1; DMY on spoils with fertiliser was 132 gm -2 yr -1). Weedy species accounted for most of the biomas, production during the first growing season. Three of the test sites were designed to study plant production on topsoils and spoils. Establishment and production of grass species were comparatively better on topsoils (30 cm in depth) than on spoils while legumes were most successful on the soils (Center test site, 1979; DMY of grasses on topsoil was 170 g m 2 yr -1 DMY of grasses on spoils was 52 g m -2 yr -1; DMY of legumes on topsoil was 20 g m -2 yr -1; DMY of legumes on spoil was 191 g m 2 yr -1). Total plant production on topsoiled (302 m thickness) plots at the South Beulah site (DMY in 1979 of 269 g m 2 yr 1) was comparable to that of native western wheatgrass prairie (DMY of 262 g m -2 yr -1). An experiment was conducted to find out if time of planting would have any effect on establishment of grasses on spoils. It was fund that late fall seeding was superior to spring planting for establishment of wheatgrasses at NB 3 test site (Control Plot, 1975: DMY on spring-seeded was 1 g m -2 yr - 1; DMY on fall-seeded was 55 g m -2 yr -1). In general, wheatgrasses (slender, streambank, thickspike and western) yielded the most aboveground biomass of all the grass species tested; yellow sweetclover was the most successful legume. Yellow sweetclover established and was productive on both spoils and topsoils but only where competition with grasses was apparently minimal. Durar hard fescue established and thrived on topsoil but dry matter production was low compared to that of wheatgrasses. Emerald crown-vetch demonstrated a potential for growth on spoils where water conditions were adequate, whereas side-oats grama, prairie sand-reed, alkali sacaton, and bird&apos;s -foot trefoil demonstrated only sporadic success. Little bluestem did not become established at any of the test sites. Peak production of the planted species, especially grasses, was generally reached by the second week of July. Legume and weed production continued to increase into late August.

Jan 1, 1982

By D. N. Nilsen

The Bureau of Mines is developing a method to recover Ni, Co, and Cu from laterites containing less than 1.2 pct Ni and 0.25 pct Co. The method consists of the following basic unit operations: (1) reduction roasting, (2) leaching, (3) solvent extraction, and (4) electrowinning. The method reflects three Bureau of Mines objectives: (1) recovery of critical minerals that are domestically in short supply from low-grade domestic laterites, (2) lower processing energy requirements, and (3) solution recycling. This report deals with the extraction of cobalt and the preparation of a suitable cobalt electrolyte by solvent extraction from liquor produced by this method. Nickel and copper are coextracted with LIX64N from an ammoniacal ammonium sulfate leach liquor containing about 1.00 g/l Ni, 0.30 g/l Co, 0.03 g/l Cu, and 0.02 g/l Zn. Cobalt (III) in the nickel-copper barren raffinate is reduced to cobalt (II) with cobalt metal. Reduction of cobalt (III) to cobalt (II) greatly aids subsequent extraction. Commercially available XI-51 extracts about 94 pct of the cobalt from the treated raffinate in one stage in a laboratory mixer-settler continuous circuit. Ammonia loaded on the solvent is removed in two washing steps. About 94 pct of the cobalt then is stripped from the XI-51 in one stage with spent cobalt electrolyte containing about 77 g/l Co and 18 g/l sulfuric acid (H2S04), Electrolytes containing less H2S04 also may be used. Preliminary data indicate that coextracted zinc may be removed from pregnant cobalt eletrolyte containing 3 g/l or less H2S04 with di-(2 ethylhexyl) phosphoric acid (D2EHPA).

Jan 1, 1980

By Seth C. Schaefer

[As part of the Bureau of Mines effort to provide thermodynamic data for advancement of mineral resources technology, the standard Gibbs energies of formation (?G°f) of MnS (manganese sulfide) and Fe0.9 S (pyrrhotite) were investigated with a high-temperature galvanic cell employing stabilized Zr02 (zirconia) as the electrolyte. Potential measurements were obtained for the cell Pt, MnS, MnO, S02 (g, 1 atm)//Zr02//02(g, 0.0114 atm), Pt with the overall cell reaction MnS (s) + 1.5 02 (g, 0.0114 atm) = MnO (s) + S02 (g) . (1) These results give the standard Gibbs energy of formation of MnS for the reaction Mn (s) + 0.552 (g) = MnS (s) (2) ?G°f = -66.487 + 15.19 x 10-3T±0.207 kcal/mole (896.4 - 1,208.1 K) (3) where temperature (T) is expressed in kelvins. Similar measurements were obtained for the cell Pt, FeO .9S, Fe304 , S02 (g, 1 atm) //Zr02//02 (g, 0.0114 atm) , Pt with the overall cell reaction 10/3 FeO .9 S (s) + 16/3 02 (g, 0.0114 atm) = Fe.,04 (s) +10/3 S02 (g). (4) These results yield the standard Gibbs energy of formation for the reaction 0.9 Fe (s) + 0.5 S2 (g) = Fe0.9 S (s) (5) ?G°f = -35.229 + 12.67 x 1073T+-0.104 kcal/mole (839.5 - 1,086.6 K). (6) A third-law analysis of MnS data yields a standard enthalpy of formation (AH°f) for the reaction Mn (s) + S (rh) = MnS (s) (7) ?H°f298 = -51.16±0.21 kcal/mole (8) A similar third-law analysis for Fe0.9S data yields a ?29°f298 for the reaction 0.9 Fe(s) + S(rh) = FeO .9S(s) (9) ?HO\°f298 = -24.01±_0.15 kcal/mole. (10) ]

Jan 1, 1980

By Ronald T. Mayerle

The Condrey Mountain RARE II area lies mostly within the Elliot Creek mining district, a significant producer of gold from placers, and gold, Silver, copper, and minor soapstone from lode deposits. No mineral production has occurred within the study area; no resources are known in the area. However, significant resources in lode and placer deposits are just outside the west and northwest boundary of the area. The Blue Ledge Mine (fig. 1, no. 15) adjacent to the western boundary, is reported to contain 226,000 ton; (205,000 t) of identified resources averaging 0.05 oz gold per ton (1.7 g/t), 2.16 oz silver per ton (/4.0 g/t), 3.5 percent copper, and 3.95 percent zinc. The mine has produced 11,131 tons (10,114 t) of ore that yielded 1,026 oz (31,908 g) of gold, 58,431 oz (1.8 million g) of silver, and 2.7 million lb (1.2 million kg) of copper. Exploration is currently underway at `he mine and vicinity, including part of the study area.

Jan 1, 1983

By Mohan K. Wali

Soil and vegetation development were studied on abandoned mine sites near Velva in Ward County, North Dakota. The sites studied were 1, 7, 17, 30 and 45 years old since abandonment; unmined sites were also studied to provide measures of comparison. Species diversity was the highest at unmined sites (114) and lowest at the I year old site (26); sites 7, 17,30 and 45 years old had 37, 52, 43 and 68 species, respectively. Stand ordination revealed that site ages were the most important in influencing species diversity and composition. Stand-environ-mental complex ordinations encompassing 53 variables showed topographic variables to be the most important followed by site ages. Rates of nutrient accumulations were as follows: organic carbon 13.1 g m-2 yr-1; nitrogen 2.5 g m-2 yr-1; phosphorus 0.01 g m-2 yr-1; potassium 0.49 g m-2 yr-1. Carbon-nitrogen ratios showed the widest range for 1 year old sites (5-40) but 70 percent of the 45 year old sites showed values below 15 which were com-parable to the unmined mixed grass prairie sites. Species distributional diagrams are provided to show their habitat preferences which may be helpful in formulating species prescriptions for revegetation.

Jan 1, 1982

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 Seth C. Schaefer

The Bureau of Mines investigated thermodynamic properties of Mn304 (manganomanganic oxide) and Mn203 (manganese sesquioxide). The standard Gibbs energies of formation (?Gf°) of Mn304 and Mn203 from their lower oxides were determined with high-temperature galvanic cells using stabilized Zr02 (zirconia) as the electrolyte. Potential measurements were obtained for the cell Pt, MnO, Mn304//Zr0 2//02(g, 0.0112 atm), Pt, with the overall cell reaction 6Mn0(c) + 02(g, 0.0112 atm) = 2Mn304(c), where- 02 refers to indicated partial pressure of oxygen at the reference electrode. Similar measurements were obtained for the cell Pt, Mn304, Mn203//ZrO2//02(g, 0.0115 atm), Pt, with the overall cell reaction 4Mn304(c) + 02(g, 0.0115 atm) = 6Mn203(c). Equilibrium oxygen pressures for the Mn0-Mn304-02 and Mn304-Mn203-02 systems were measured and may be expressed for the respective systems as [23,400 109 P02 T + 11.91 (764.9 - 1,208.6 K) and log p02 = - 11,957 + 9.66 T (968.6 - 1,208.2 K),] where pressure (p02) is in atmospheres and temperature (T) is in kelvins. Standard thermodynamic properties of Mn304 and Mn203 were derived from these measurements and auxiliary thermodynamic data from the literature.

Jan 1, 1982

By L. A. Haas

The U.S. Department of the Interior, Bureau of Mines, is conducting laboratory-scale research to determine the leaching conditions required with sulfuric acid for extracting base metal from a matte with a copper-to-nicke1 ratio of 6 to 1. The matte (61.2 pct Cu, 9.7 pct Ni, 3.3 pct Fe, 21 pct S, and about 5 oz of precious metals per ton) was prepared from Duluth Complex (Minnesota) ore by smelting a bulk sulfide flotation concentrate. The matte was pre leached at atmospheric pressure to selectively extract 20 pct of the nickel, and the undissolved solids were referred to as the matte residue. Autoclave leaching of the matte residue extracted over 95 pct of the nickel, copper, and iron. The remaining leach residue in the autoclave contained over 100 oz of precious metals per ton. The leaching conditions required were matte grind of greater than 98 pct minus 325 mesh, pulp concentration of 50 g/1, total pressure of 100 psig with oxygen at 150° C or 400 psig with air at 180° C, 50 g/1 H2S04, 700 rpm agitator speed, and 6 hours of leaching time. The leaching time was decreased to 2 hours by increasing the agitator speed to 1,300 rpm. Sulfuric acid concentration greater than 50 g/1 did not appreciably enhance the base metal extraction, but with less acid, residues with higher iron concentrations were obtained. Supersaturation of the liquor was prevented at 150° C by using a 1ixiviant that contained 30 g/l Ni and 20 g/1 Cu.

Jan 1, 1979

By Joseph W. Town

The Bureau of Mines conducted studies related to SO2 air pollution to determine attritioning rates, SO2 sorption rates, and sulfur loads that could be obtained on commercial alkalized alumina sorbent pellets. Fluidized-bed attritioning rates ranged from 0.025 pct/hr for alkalized alumina with a crushing strength of 4 kg to 0.075 pct/hr for 0.5 kg crushing strength mate¬rial. Airlift attritioning rates ranged from 0.50 pct/hr for 3 kg crushing strength alkalized alumina to about 3 pct/hr for 0.5 kg material. Attritioning rates for the commercial alkalized alumina were comparable to those obtained for sorbent pellets prepared in the Bureau of Mines laboratory. Sorption rates were related to S02 concentration in flue gas, temperature, and presence of nitrogen oxides in the gas stream. Sorption rates at 300° C were 0.35 X 10-6 gS/gp/sec (grams sulfur per gram pellet per second) in 0.045 pct so, gas, 5.1 x 10-5 gS/gp/sec in 0.34 pct SO2 gas, and 65 X 10-5 gS/gp/sec in 10 pct SO2 gas. For the 0.34 pct S02 gas, sulfur loads of 0.10 gS/gp (the projected load for regeneration) were obtained in 47 min at 130° C and in 116 min at 300° C. The presence of either NO or NO2 in the 0.34 pet S02 gas increased the SO2 sorption rates 2 to 3 times at 300° C, but had no effect at 130° C.

Jan 1, 1969

By R. E. Mussler

As part of an overall goal to develop technology that can maintain an adequate supply of minerals to meet national economic and strategic needs, the Bureau of Mines is evaluating a method for selectively extracting nickel and cobalt from low-grade domestic laterites. The method involves electrowinning to recover the metals in pure form; therefore, preliminary laboratory-scale electrowinning tests were conducted in both a nondiaphragm and a diaphragm cell to determine the effect of variables on energy efficiency under controlled conditions. Electrolytes were generally reagent-grade sulfate solutions that were prepared to simulate electrolyte that could be obtained by stripping nickel-and cobalt-rich solvent extraction reagents. Limited tests were conducted with electrolyte generated from laterite leach solutions. Electrical energy consumption in a nondiaphragm cell was 2.06 kwhr/lb Ni with the cell operated at 50° C, a cell feed of 90 g/l Ni, a pH of 3.5, an extraction of 3.2 g/l, and a cathode current density of 20 amp/ft2. The energy requirement decreased with increasing concentration and temperature, and increased with increasing. extraction and current density. At 50° C, energy consumption in the nondiaphragm cell was 21 pct greater than in the diaphragm cell, but it was only 5 pet greater at 65° C. For this reason and because of overall cost considerations, operation at 65° C with the nondiaphragm cell was preferred. Smooth sheets of cobalt were obtained by electrowinning in a nondiaphragm cell at selected temperatures from 50° to 85° C and with cobalt concentrations from 55 to 87 g/l. The energy consumption (1.48 kwhr/lb) was 22 pet lower with a cobalt concentration of 75 g/l and a cell temperature of 65° C than with a cobalt concentration of 55 g/l and a cell temperature of 50° C.

Jan 1, 1981

By T. G. Carnahan

The Bureau of Mines conducted laboratory-scale weathering research on a leach residue containing elemental sulfur and mixed metal sulfides. Experiments were performed to determine pH and impurity element concentrations in the effluents as functions of time and to determine the effects on effluent concentrations of mixing the residue with dolomite tailing material. Four 800-day tests were conducted simultaneously. Soluble metal concentrations, especially zinc and copper, were excessive in the effluents from washed and unwashed samples of the residue. Concentrations of up to 20 g/l of Zn and 12 g/l of Cu were obtained. The pH values of the unwashed and washed residue effluents at the completion of the experiments were 2.8 and 1.9, respectively. Sulfuric acid from oxidation of pyrite caused the pH decrease. Mixing unwashed residue with dolomite tailing to maintain a near-neutral pH minimized the heavy metals content in the effluents. The pH in the dolomite tests increased slowly after the first 360 days and attained values of 7.8 and 8.2, respectively, for tailing containing 1 pct leach residue and for tailing devoid of leach residue. Dissolved zinc and copper did not exceed 0.10 g/l of Zn and 0.001 g/l of Cu.

Jan 1, 1982

By H. H. Storch

"INTRODUCTION The first paper of this series contained data concerning the behavior of polyhalite (K2S04.MgS04.2CaS04.2H20) upon calcination and subsequent leaching with water at 100° C. It was found that upon heating polyhalite to temperatures between 298 and 500° C. the water of crystallization is driven off, leaving, an amorphous mixture of K2S04, MgS04, and CaS04. Two transition points were located; one at 298° C. which coincides with the vigorous evolution of steam; and one at 551° C. which results in the formation of a hard mass of crystals. The latter probably consist of a solid solution If the compounds langbeinite (K2504, 2MgS04), potassium dicalcium sulphate (K2304. 2CaS04), and anhydrite (CaS04). The heat of decomposition of polyhalite at 298° C. was measured and found to be 66,000 ± 5,000 calories per mol. The optimum temperature of calcination with regard to subsequent extrac¬tion with two parts of water (at "" 0° C.) is 430 to 450° C. for 65 to 100 mesh material, if one half hour at the calcination temperature is allowed. The maximum concentration of K2S04 obtainable in the extraction of calcined polyhalite is 11.4 grams per 100 grams of water. This concentration of K2304 is considerably above the equilibrium value (3.6 g. per 100 L. of H20 at 83° C.) with respect to the solid phases polyhalite, potassium calcium pentasulphate, ¬and anhydrite. The figure 11.4 K. of K2804 per 100 g. of H20 is also somewhat than the equilibrium value (9,65 g. per 100 g, H20) with respect to the solid phases potassium calcium pentasulphate and syngenite."

Oct 1, 1930

By S. R. Droes

The U.S. Bureau of Mines investigated calcium fluoride (CaF2) assisted sulfuric acid (H2S04) leaching as an alternative to the melting-quenching procedure to obtain Mn from domestic manganese silicate resources. Pyroxmangite [(Mn, Fe) Si03] ore containing, in percent, 34.4 Mn, 22.8 Si, 2.6 Ca, and 1.3 Fe was leached in a 500-mL resin kettle. Ninety-six percent of the Mn was extracted under conditions of 330 g/L ore, 245 g/L H2S04, 35 g/L CaF2, 90&apos; C, and 2 h. To incorporate electrowinning in recovering Mn, the ore was leached with a simulated spent anolyte solution containing, in grams per liter, 12 Mn, 140 H2S04, 130 (NH4)2S04 (ammonium sulfate), and 5 CaF2. Manganese extraction of 92 pct was achieved from 130 giL ore leached at 90° C in 3 h. The Fe, silica (SiOJ, and other impurities were precipitated from the pregnant solution by neutralization with ammonia (NH3). Manganese of greater than 99-pct purity was deposited at a cathode current density of 50 mA/ cm2 at 30° C, with a current efficiency of 65 pet in a two-compartment cell. A flowsheet was proposed for the leaching and electrowinning procedure.

Jan 1, 1990

By W. L. Staker

Alternatives were developed to the conventional ammoniacal carbonate leaching-steam stripping procedure for recovering copper as an oxide from contaminated scrap metal. By entraining air bubbles in the leach solution, the copper dissolution rate was increased to 1.5 g/in2 of copper surface per hour, compared to 0.5 g/in2/hr produced by conventional agitation in stirred tanks. Using entrained nitrogen gas bubbles for agitation in conjunction with powdered sulfur not only resulted in rapid dissolution but also simultaneous precipitation of the copper from solution as a high-grade cuprous sulfide.

Jan 1, 1971

By Kenneth P. V. Lei

The Bureau of Mines investigated a silver-catalyzed oxidative procedure for leaching an arsenical copper sulfide concentrate containing 10 pct As and 32 pct Cu_ Currently, there are no environmentally safe means to treat arsenical copper concentrates in the United States. Leaching was conducted in a 2-L autoclave reactor. The effects of catalyst concentration, O2 pressure, temperature, and H2S04, Cu, As, and Fe concentrations in the leaching solution on extractions of metals from the concentrate were determined. The best leaching conditions for extracting 95 pet eu and As and less than 21 pct Fe were 260 g/L concentrate, 0.007 mol/L (1.0 g/L) AgCI, 3.0 mol/L (294 gIL) H2S04, 1000 C, 60 psig 02, and 6 h. Copper as CuS04-5H20 was recovered by crystallization from the pregnant solution. Arsenic, as AS203, was recovered from the copper mother liquor by solvent extraction, with tributyl phosphate, S02 reduction of As5+ to As3+ in the strip solution, and crystallization of the As3+. The silver catalyst was recovered by contacting the leached residue with a brine solution. A conceptual scheme is proposed for treating arsenical copper sulfide concentrates.

Jan 1, 1987

By D. N. Nilsen

The Bureau of Mines is investigating a method to recover Ni, Cu, and Co from low-grade domestic laterites through reduction roasting, leaching, sol-vent extraction, and electrowinning unit operations. The objective of this research is to develop processing technology that can convert low-grade domestic deposits containing critical metals into national reserves. As a part of this research, a solvent extraction system was investigated for the extraction of nickel and copper, followed by the separation and production of suitable electrolytes. Nickel and copper were coextracted from ammoniacal ammonium sulfate leach liquors (pH~9.5) with LIX 64N extractant in a laboratory-size mixer-settler continuous circuit. Three extraction stages resulted in >99-pct extraction of nickel, substantial copper extraction, and essentially no cobalt extraction from leach liquors. A crowd stage reduced the ammonia loading on the solvent by maximizing nickel loading. Residual ammonia was removed from the loaded solvent with a pH-controlled scrub. Nickel and copper loaded on the solvent were separated by selective stripping. Typical nickel strip circuit operation using electrolyte containing 90 grams per liter (g/l) Ni and 11.9 g/l H2S04 yielded >99.9 pct Ni stripped from the solvent in five stages. The copper loading on the recycled solvent was controlled in a copper strip stage using electrolyte containing 25 g/l Cu and 160 g/l H2S04,

Jan 1, 1981

By Seth C. Schaefer

As part of the Bureau of Mines, U.S. Department of the Interior, effort to provide thermodynamic data for the advancement of minerals technology, the Gibbs energy of formation of sphalerite (zinc sulfide) was investigated with a high-temperature galvanic cell employing stabilized zirconia as the electrolyte. In the temperature range 948 to 1,210 K, potential measurements were obtained for the cell Pt, ZnS + ZnO, S02 = 1 atm // Zr02 // Cu20 + Cu, Pt, with the overall cell reaction ZnS(c) + 3 Cu20(c) = ZnO(c) + 6 Cu(c) + S02(g). (1) These results, combined with the best available values of ?Gf° for ZnO, S02, and Cu20 from the literature, give the Gibbs energy of formation of zinc sulfide for the reaction Zn(l,v) + 1/2 S2(g) = ZnS© (2) ?Gf° = -64.223 + 24.02 X 10-3T ± 0.650 kcal/mole (3) (948-1,180 K; standard states - pure liquid zinc and S2 gas at 1 atm), and ?Gf° = -92.720 + 48.17 X 10-3 ± 0.650 kcal/mole (1,180-1,210 K; standard states - pure zinc vapor and S2 gas at 1 atm). A third law analysis yields for the formation reaction Zn(1) + 1/2 S2(g) = ZnS(c), (5) a standard enthalpy of formation as follows: ?Hf298.15 = -63.64 ± 0.700 kcal/mole.

Jan 1, 1978