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By L. L. Wyman

SINCE the observations of Heyn,1 relative to the embrittlement of copper after having been heated in hydrogen, this subject has received considerable attention from later investigators. The published works of Archbutt2 and of Bengough and Hill3 give the reasons for this embrittlement-the formation of steam by the reaction between cuprous oxide and hydrogen. From Ruder,4 Pilling,5 Moore and Beckinsdale,6 Bassett and Bradley,7 and from Smith8 can be obtained quantitative data concerning the action of hydrogen and other reducing gases on copper samples having various oxygen contents. This problem has been discussed from a practical standpoint by Fuller9 who calls attention to some of the instances of this embrittlement encountered in the manufacturing field. The examples he cites may be considered typical cases of copper embrittlement which were incident to the process of manufacture. In many cases, such difficulties are overcome by changes in the manufacturing process.

Jan 1, 1931

By L. L. Wyman

SINCE the presentation, by the writer, of the initial paper on the embrittlement of copper,1 the subject has been investigated further along two separate lines. The first series of investigations involves the "double-deoxidized" copper, while the second series is devoted to single deoxidizers other than those used in the investigations reported upon last year. The object of these experiments is to develop a type of copper that will show the minimum of detrimental effects after having been exposed to alternate oxidation and reduction. The fabrication of this material necessitates the use of alternate oxidizing and reducing atmospheres, at temperatures ranging up to 900° C. Following this treatment it is essential that the soundness and strength of the copper be unimpaired, even in sections of only a few thousandths of an inch in thickness.

Jan 1, 1932

By L. L. Wyman

PREVIOUS studies1 by the writer dealing with the embrittlement of copper have been concerned with the behavior of various pure and deoxidized coppers when exposed to an oxidation-reduction cycle, and the consequent evaluation of these materials on the basis of their resist-ance to this action. No attention was devoted to the variations in pene-tration of embrittlement with time, when these copper materials are exposed to a strong reducing gas, such as hydrogen, nor to the variations in oxygen penetration, with time and temperature, into the "pure" coppers. The cause of the embrittlement is the reduction of the oxygen in the copper by the hot reducing gas, so that a consideration of time, tempera-ture, the occurrence of hydrogen and oxygen must be given. For the purpose of differentiating some of "the involved factors, the present work may be divided into two separate series of experiments. The first of these deals with the oxidation of purified coppers under various conditions and then the subjection of these to a standard hydrogen treatment. The second series concerns the reduction, under different conditions, of tough-pitch coppers of several oxygen contents. The resulting data will give the rates of oxidation, and of reduction, for the materials involved. The first series of experiments will reveal how rapidly copper may become oxidized, while the second series will indicate how rapidly embrittlement will penetrate into an oxygen-containing copper when it is exposed to hydrogen at different temperatures.

Jan 1, 1933

By L. L. Wyman

THE resultant embrittlement caused by the exposure of oxygen-bearing copper when hot and exposed to reducing gases has been the subject of many studies.1 Little attention, however, has been given to the possible embrittling effects due to atmospheres or conditions that under some circumstances might be the source of a reducing gas. At rather infrequent intervals there occur reports of copper becoming embrittled during normal annealing cycles in commercial steam-atmos-hered furnaces such as customarily are used for this operation. As might be expected, several other factors exist-such as oil, dirt on the wire, or in the furnace, or metallic surface contacts that might produce reducing gases and be the source of the trouble. However, in consider-ation of the statement made by Ruder,2 it would seem that under some conditions steam itself might prove to be the source of trouble. A consideration of the amount of the dissociation of water vapor up to temperatures of the melting point of copper shows that' the amount of hydrogen that could come from this source is far too minute to account for any embrittlement. What such information does not tell is what will happen at the surface of copper when subjected to steam at elevated temperatures, for entirely different conditions may persist, which would account for Ruder's observation. Furthermore, there are no data as to what might happen at the surfaces of other materials present, the result-ant of which might affect the condition of the copper present. For this reason, it was decided to make a series of experiments com-parable to those previously conducted by the writer,1 which would clarify the effect of the steam on copper, and in copper in the presence of steel.

Jan 1, 1940

By E. P. Wiechrnann, C. M. Castro, G. A. Vidal

In copper Eta plants the optimal current density setpoint depends on the electrolyte composition and temperature. However, conventional plants operate with large standard deviations. A value of 14% with current densities offsets up to ±50% is typical. For worst, during opencircuit or shortcircuit events this variation can be from -100% to +200%. Naturally, energy consumption and copper quality are compromised. Several devices have been successfully employed to reduce set point deviations. Last developments include; Optibar Segmented Intercell Bars, Outotec Electrodes Arranging Method and NTC Selective Electrodeposition Enhancers. This paper researches and compares these technologies. It is shown that short circuits can be effectively reduced in occurrence and magnitude. Moreover, 95% of the electrodes can be forced to operate within ±10% of the set point. The specific energy consumption is reduced from 2,000 KW per Ton to values close to 1,900 KW per Ton.

Jan 1, 2011

By Y. Topkaya, R. E. Johnson, B. R. Palmer, R. B. Bhappu, A. E. Clark, R. P. Bush, L. E. Schultze

The U.S. Bureau of Mines conducted copper exchange capacity (CuEC) tests for six common clays under simulated in situ leaching conditions. Regression equations were obtained from the data expressing the CuEC as a function of Cu concentration, pH, and temperature. Further testing resulted in regression equations expressing CuEC's of Na and Ca montmorillonites and attapulgite as a function of Cu concentration, pH, and the concentration of metal ions which compete with Cu for exchange sites. Using these equations, an analysis was made of the impact each clay could have on overall copper recovery. The results suggest that Ca and Na montmorillonite clays could have a major impact on Cu recovery and that attapulgite and illite clays could have a smaller, but still significant, impact. Kaolinite and ripidolite clays pose little threat to loss of copper from in situ leaching solutions. Copper losses are decreased by the presence of competing ions, and A1 and Mg have the largest impact of those ions normally present in Cu leaching solutions.

Jan 1, 1993

By R. S. Forgan

The synthesis and study of a systematic series of phenolic oximes have shown that substitution in the 3-position can greatly affect extractive efficacy. Solid state, solution and gas phase analytical techniques, including X-ray crystallography, EPR and IR spectroscopy and collision induced dissociation mass spectrometry have been assessed for their applicability in interpreting the origins of differences in extractant strength. The dominant substituent effect on pH0.5 is the change in ligand pKa, with the more acidic ligands being stronger extractants. The influence of the 3-substituent on the stabilising intracomplex H-bonding of their copper(II) complexes also affects extractant strength. The 3-NO2 substituted ligand shows the lowest pH0.5 value, due to a combination of its low pKa and a stabilising bifurcated H-bond assembly around the copper(II) centre. Appending an aminomethyl group to the 3-position gives a ligand capable of binding a metal and its attendant anion. These metal salt reagents show potential to open up new flowsheets for the processing of high tenor copper feeds.

Jan 1, 2007

By R. F. Hammen

Copper is one of the most widely used metals in industrial processes and is also present in most mining operations. Extraction of copper from solutions often proves difficult due to the presence of complexing agents. ChromatoChem, Inc. has developed a Solid Phase Extraction (SPE) support (HiPAC) for removal and recovery of metals from wastewater. The HiPAC SPE support employs chelating agents covalently coupled to a long linker molecule. Several solutions containing copper and complexing agents were tested including 1) copper and carbonate, pH 9.8, 2) mixed metals and anions with copper and cyanide, pH 11, and 3) copper and the chelating agent EDTA, pH 11. The copper was extracted from solutions one and two at high pH, but the EDTA containing solution needed the pH lowered to make the copper available for capture. In each example, the copper concentration was significantly reduced by HiPAC SPE treatment.

Jan 1, 1994

Copper Extraction from Scrap Cables by Biotechnological Means

Sep 13, 2010

By E. E. Caba

Copper smelter flue dusts containing arsenic are hazardous materials requiring environmentally accept-able disposal, preferably with re-source recovery under the RCRA and CRCLA regulations. However, the known resource recovery processes entail capital and operating costs greater than can be justified by the revenue of the recovered metal. Consequently, the smelting industry is tending to forego resource recovery in favor of encapsulation and storage in a certified class I hazardous waste site, or in a dedicated facility located at the source Superfund site. Order of magnitude costs for this option with portland cement encapsulation are estimated at $100 per ton, not including transportation. Industrial adoption of a new resource recovery process re-quires that its cost, including capital amortization, exceed the cost of encapsulation and storage only by the amount of the offsetting revenue from sale of metal. The lime-roast/ammoniacal leaching process is expected to meet this goal.

Jan 1, 1992

By Zhi-biao Yin

Copper smelter flue dusts often cannot be directly recycled to the smelting process and accumulate as hazardous wastes requiring environmentally acceptable disposal. Because of the limited amount of flue dust, a separate copper extraction process must be simple and require-a small plant investment. A flue dust process has been developed, consisting of the following steps: (1) roasting a pelletized mixture of hydrated lime and flue dust to fix arsenic and sulfur as insoluble calcium salts, (2) heap leaching the roasted pellets with a buffered ammonia/ammonium salt solution to extract copper as an ammine complex in a lined cell that is the final repository of the leached pellets, and (3) boiling ammonia from the lixiviant to precipitate copper. Condensed ammonia and the filtered solution are returned to leaching. Heap leaching in the final repository cell lowers the capital investment significantly compared with competing extraction processes. Chemistry with respect to arsenic, sulfur and copper is discussed.

Jan 1, 1992

By W. G. Davenport

Changes in copper extraction from 1960 till today are documented. The top ten changes have been: (a) replacement of reverberatory smelting by high intensity oxygen rich smelting (b) growth of the Outokumpu flash smelting to over 50% of the world's smelting capacity (c) successful development of single furnace coppermaking but only for low slag fall concentrates (d) replacement of the batch Peirce-Smith converter by continuous converting, but only in a few cases (e) increased SO2 capture throughout the industry, mainly-as sulfuric acid (f) development of low initiation temperature `big bight' Cs catalysts for treating the continuous high-SO2 strength gases from continuous smelting/converting (g) complete replacement of reverberatory anode scrap and cathode melting furnaces by the Asarco shaft furnace (h) adoption of stainless steel permanent cathodes and automated stripping technology for electrorefining and electrowinning (i) complete elimination of wire bar casting by continuous bar casting/rod rolling (j) development and adoption of extractants for turning weak impure leach solutions into strong pure electrolytes. It is postulated that the biggest possible change over the next 20 years would be complete replacement of smelting/converting by hydrometallurgical processing. However, this seems unlikely due to copper purity, precious metal recovery, and economic concerns. The increasing value of sulfuric acid to many copper companies gives chalcopyrite smelting/oxide-supergene leaching a nice synergy especially with the energy credits now coming from continuous smelters, and their acid plants.

Jan 1, 1999

By Segnit E. R

Results are reported of a study of the reactions occurringin the combustion of chaIcopyrite particles underconditions simulating those in the shaft of a flashsmelter.The reactions were studied using kinetic and mineralogicaltechniques. Reactions. rates above 500°C wererapid, most of the reaction taking place in less than 50ms. Final products were copper-iron ferrites with spineltype structures. Probable reaction mechanisms are discussed.

Jan 1, 1977

By Lars O. Werme

Already the KBS Project proposed copper as a suitable material for encapsulation of spent nuclear fuel. The basis for this choice was the thermodynamic stability of copper in water and the fact that deep granitic groundwaters in Sweden are oxygen free. With a limited supply of oxidants, a copper canister would have the potential for a very long service life. The research and development work aiming at encapsulating nuclear fuel entered a new phase in 1993, when SKB launched its Encapsulation Plant Project. Within this project, SKB has: ? designed a facility for encapsulation of nuclear fuel, ? laid down the design premises for a canister for disposal of nuclear fuel, ? tested and developed fabrication methods for copper canisters, ? evaluated the long term chemical and mechanical behavior of the canister, ? made preliminary plans for a factory for the production of copper canister, ? constructed a canister laboratory for full scale testing of the key operations in an encapsulation plant. The conclusions of this project were that a canister consisting of an outer layer (50 mm) of copper over an insert of cast nodular iron would provide sufficient corrosion protection and would have sufficient mechanical strength. This canister can be produced by several methods of which forming from rolled plates, hot extrusion, and "pierce and draw" have been tested at full scale. The canister will be sealed by electron beam welding in the encapsulation plant, and the integrity of the weld will be verified by ultrasonic testing and' high-energy radiography. The final development work in this area will be performed in the canister laboratory.

Jan 1, 1999

By Albert W. Spitz

Profitably recovering copper and precious metals from copper bearing scrap is a demanding and frustrating combination of art, science and economics. With fluctuating markets, varying raw materials and increasingly stringent environmental regulations requiring process revisions, practically everything is changing. The volatile copper market constantly shifts the percentage of copper in the scrap that can be economically processed. Scrap that has value one day may incur a disposal cost the following day. Also with less copper in the scrap, more residuals, slag, fume, etc. are generated which frequently present disposal problems and infrequently generate income. The ever increasing amounts of electronic scrap add value to the copper produced by virtue of the precious metals present. Printed circuit board materials create more slag and organic off gases which must be treated. Finally, the emphasis on reducing emissions of organics and other metals, especially lead, is a continuing challenge. Stack gases, fugitive emissions and ambient air quality all demand constant surveillance.

Jan 1, 1997

By Alan James Parker

Chalcopyrite can be converted to pure copper by the following five steps. An exothermic sulfation roast of chalcopyrite; leaching of cupric sulfate from the calcine with dilute acid; precipitation of Chevreul's salt and or other copper sulfites with ammonium sulfite or precipitation of crude copper by autoclaving ammonium sulfite and cupric sulfate at 150°C; dissolution of Chevreul's salt, or the crude copper, as cuprous sulfate, using acidic cupric sulfate in an acetonitrile-water solution as oxidant; precipitation of pure copper by thermal disproportionation of the cuprous sulfate solution. Acetonitrile and acidic cupric sulfate solution recycle. Advantages over conventional processes include lower cost, lower energy consumption as waste heat, sulfur removal as ammonium sulfate or gypsum, rather than as sulfur dioxide and rapid throughput. The net reaction is: 2 CuFeS2 + 4H20 + 15/2 02 + 8 NH3?2Cu + 4 (NR4)2 SO4 + Fe2O3

Jan 1, 1976

By C. J. Burkhalter, H. Andrade, T. C. A. Gardner, J. P. Campbell

During the 1990’s several copper heap leach facilities treating crushed and agglomerated oxide and sulfide ore were constructed in South America. The majority of these facilities have been in operation for at least three years, during which time the operators have been able to monitor the performance of the heaps. The basis for the paper is a compilation of these operators’ experiences, leading to a discussion of the lessons learned over the past decade. Several key geotechnical issues are examined, focusing upon the integrity of the ore, drainage material and pipe network, along with the success of any inter-lift liners.

Jan 1, 2002

By J. G. Jenkins

Magma Copper Co.'s San Manuel solvent extraction/electrowinning (SX-EW) facility has operated since May 1986. The original facility had a design capacity of 22.6 kt/a (25,000 stpy) of electrowon copper cathode produced by processing pregnant leach solution from an open pit-heap leach operation. In 1988, the plant was expanded to 45.3 kt/ a (50,000 stpy) to incorporate processing in-situ leach solutions. This pager focuses primarily on the heap leaching area with regard to exploration, testing, feasibility, permitting, design and construction, and operating practices. Research using surfactant leaching aids to enhance copper recovery is also discussed.

Jan 1, 1995

By C. Salcedo, J. Vallance, J. Sáez, M. Robles, J. Spangenberg, S. Rosas, L. Fontboté

The Tambomachay ore deposit (13°28'36.78"S, 71°57'35.98"W, about 6 km north of the town of Cuzco, Peru) consists of Cu hosted in arkosic red beds of the Kayra Formation (Lower Eocene). Bornite, chalcopyrite, chalcocite, covelite, digenite, malachite, and chrysocolla occur disseminated in thin layers and in veinlets. The occurrence of the copper ores in a part of the red bed sequence containing green reducing layers, the presence of organic matter in interstices between the hypogene sulfides, and the sulfur composition of the copper sulfides (δ34S values between -16.9 and -12.4‰ vs VCDT) pointing to bacterial sulfate reduction, are strong arguments to propose that mineralization was caused by copper-bearing oxidizing saline basinal fluids that precipitate copper sulfides when they meet reduced sulfur in an organic matter-rich horizon. Faults parallel to the regional Tambomachay Fault could have acted as feeders for oxidizing basinal copper-bearing fluids. Fluid migration was probably driven by tectonically-induced topography gradient. INTRODUCTION A number of red bed Cu occurrences are known in the Cuzco region in the early Eocene – early Oligocene San Jerónimo Group (Gregory, 1916; Carlotto et al., 1996, 2011; Loza et al., 2004). In the past, copper ores were extracted in several small-scale mines in the surroundings of Cuzco, including Tambomachay, Tipón, and Zurite in the Cusco province and Ushpa, Guilda, Giovanna, and Langui in the Sicuani Province. The abandoned Tambomachay Mine (13°28'36.78"S, 71°57'35.98"W), about 6 km to the north of the town of Cuzco (Romero et al., 2015; Salcedo et al., 2017, Fig. 1) was chosen as the main site for the present research aimed to better study the genesis of these copper occurrences. Results deriving from fieldwork, microscopic characterization of ore and host rock, and sulfur isotope determination suggest that the key factor for the genesis of the copper ores is that copper transported by oxidizing basinal fluids is trapped by reduced sulfur of bacteriogenic origin located in a part of the red bed sequence that shows intercalatins of green reduced horizons.

Jan 1, 2019

By Archie W. Fletcher, R. J. Wesely, Nathaniel Arbiter, A. D. Zunkel

In contrast to pyrometallurgy's six thousand year history in the production of metals, that of hydrometallurgy is of relatively recent origin. The earliest reference to it at all was in the 16th century, with the first applications to copper in the 17th and 18th. In the 19th century, increased demands for pure metal resulted in development of electrolytic refining, and early in this century electrowinning. The rapid growth in wpper production in the present century, paricularly in the United States and Chile, stimulated the development of new technology for leaching, and for the recovery of copper from leach solutions. Solvent extraction has become a major factor during the past quarter century by permitting novel leaching technology which produces dilute or complex solutions. In addition, solvents other than sulphuric acid, and chemical methods for precipitating copper metal are now of increasing interest. These are trends which should grow in importance in the future with the need to process lower grade and more complex materials. The evolution of copper hydrometallurgy is reviewed briefly and key factors in recent major developments are presented with details of specific operations and with trends for the future indicated. The relative importance of copper hydrometallurgy is compared to that of pyrometallurgy in the light of probable changes in ore supplies and character.

Jan 1, 1993