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By E. L. Frueh

AMAX Base Metals Research & Development, Inc. has developed a process for treating copper-nickel mattes to produce copper cathodes and a pure nickel sulfate solution. In this process, the input matte is preleached in a copper sulfate electrolyte bleed solution so as to dissolve nickel from the matte and cement copper from solution. The preleach leaves a substantially pure nickel sulfate solution. The residue from the preleach is roasted to less than about one percent sulfur. A portion of the calcine is leached with sulfuric acid to make a copper sulfate solution for input to the tank house. The residue from this leach and the remaining calcine are smelted to form a bimetallic (copper/nickel.) anode. The anodes are electrolytically refined and copper is preferentially deposited on the cathode while the nickel reports to the electrolyte, A bleed stream is taken from the electrolyte and used in the preleaching of the input matte. This process produces high purity metal streams while consuming less energy and smaller amounts of reagents as compared with other matte processes.

Jan 1, 1983

By R. E. Johnson

The No. 3 reverberatory furnace at Phelps Dodge. Corporation's Morenci, Arizona copper smelter first received oxygen from a new oxygen plant during October 1982 and began operation with oxygen-fuel and oxygen sprinkle smelting burners which burn concentrate with oxygen. The furnace was completely converted to roof-mounted oxygen-fuel firing in October 1982. All conventional air-fuel bridge wall burners were extinguished at that time. The novel arch-mounted oxygen sprinkle smelting system began continuous operation April 1983. Since startup, unit fuel requirements decreased and furnace throughput significantly increased. Furnace off gas SO2 strength increased from an average of 1.5% SO2 to an average of 20% using only oxy-fuel burners. Oxygen sprinkle burner operation also has given excellent results, with the furnace off gas strength increasing to 35%-60% S02. There has been a reduction in overall arch temperatures, an increase in matte and slag temperatures, and a lowering of furnace bottom buildup with oxygen smelting. Furnace off gas is blended with converter off gas and treated in a sulfuric acid plant.

Jan 1, 1983

By Ph. Cauwe

This paper presents the experience that NESA and MECHIM have gained about recovery of non ferrous and precious metals from complex sulfide materials. Processed materials are from natural deposits or metallurgical by-products or residues. Roasting of these materials is closely related to the pyro or hydrometallurgical processes used downstream of the roasting. Conditions of a first step of roasting the SELECTIVE ROASTING, are analyzed and explained. The roasted products so obtained are characterised by an extended elimination of volatile sulfides (AS, Bi, Sb, Sn, Pb, Hg, ?? ) and are readily available for the pyrometallurgical recovery of non ferrous and precious metals. After the SELECTIVE ROASTING, thanks to. the high porosity obtained in the "selective calcine", the SULFATE ROASTING is per-formed in excellent conditions. Hydrometallurgical tests performed for the final calcine show a high recovery of non ferrous and precious? metals and require only simple and well known processes. Many experimental and commercial data are given.

Jan 1, 1983

By Shinya Otsuka

Activity coefficient of oxygen in sulfide-rich and metal-rich melts in copper-sulfur binary were determined at 1423 and 1523 K by means of a modified coulometric titration technique using the following cell: 0 ( is Cu-S melts) I Zr02 (+Ca0) I air, Pt The activity coefficient values obtained in the present study increase rapidly with sulfur composition in the vicinity of xs = 0.3333. The data obtained for the matte saturated with the metal-rich melts are in good agreement with those obtained by Kuxmann and Benecke, Schmied 1, and Eguchi and Yazawa. Those obtained for the metal-rich melts are in good agreement with the results of Sano and Sakao.

Jan 1, 1983

By C. Ek

In bismuth metallurgy, low-copper high-sodium mattes are by-produced. Different charges containing mixtures- of crude mattes, oxidized matte, and/or copper sulfide concentrate and/or copper silicate ore have been smelted to give a rich matte and a disposable slag, then converted to obtain blister copper with high recovery and a rich slag to be recycled.

Jan 1, 1983

By Peter Fischer

A demonstration plant for QSL technology with a continuous through-put of up to 10 t/h concentrate has been in operation at the Berzelius smelter, Duisburg, Germany since early 1981. In the QSL-process, both oxidation and reduction steps are performed in a single horizontal long cylindrical reactor. In the present demo-reacior, 2.5 M diameter by 22 M long, these steps are separated by a low partition wall with an underflow opening, to prevent backmixing of slag. -Tests on a variety of concentrates, including high-lead Missouri-type material and lower grades, have shown recoveries and consumables indicating very attractive economics. Investment cost estimates further enhance the economic attractiveness. Environmental protection afforded by the QSL system is a major advantage. The process has proven its reliability and versatility and is now ready for commercialization. Continued test work, including smelting secondary lead materials, is planned.

Jan 1, 1983

By A. R. Udupa

The reduction roasting behavior of chalcopyrite has been investigated using various combinations of a desulfurizing agent, i.e., CaO or Na2CO3, and a reductant, i.e., CO, H2 or C. Using these, combinations the sulfur is removed from the mineral as CaS or Na2S rather than SO2 as is the case with conventional copper smelting and converting. The laboratory reduction ex¬periments were conducted using thermogravimetric analysis (TGA) and boat tests of mixed combinations of fine particulate reactants subjected to a continuous gas stream. The degrees of metallization were determined by both weight loss and chemical analysis methods and the products examined using optical and scanning electron microscopy and electron probe microanalysis. The percent reduction after one hour at 900°C ranged from 60% to 94%. From these data It was possible to provide postulations as to the controlling reduction mechanisms.

Jan 1, 1983

By M. Hashimoto

The equilibrium distribution ratios of sulfur between molten copper and CaO-fluxes containing caF2 and caC12 were determined in the range of 1300° to 1400° C under carbon monoxide. The rate of approach to equilibrium is rapid and increases with increasing CaCll concentration. In CaO-CaFl-CaCl2 fluxes, the distribution ratio varies in a complex way with temperature and CaFl concentration. The results are compared with those obtained with the binary fluxes of CaO with BaFZ and MgFl ?

Jan 1, 1983

By J. C. Yannopoulos

The quest for a continuous copper smelting and converting process, which has been going on for a long time, has not as yet reached its objective. The most recent efforts for the development of a continuous copper?making process started about two decades ago. Among the contending proposed processes, four have been piloted and three of them are currently in operation: the WORCRA process., the NORANDA process, the MITSUBISHI process, the OUTOKUMPU process. The WORCRA process, after some long pilot plant tests, failed to develop as an industrial process: The NORANDA process, as currently operating, is a smelting process and not a continuous copper?making reactor as initially conceived. The MITSUBISHI, although the only continuous process, has not been widely accepted. The OUTOKUMPU process can be applied only to a low iron concentrate feed and co?produces blister and high in copper slag. The thermodynamics of these "continuous" systems and the practical problems of their industrial application are reviewed and discussed. The achievement of efficient and inexpensive environmental control should' be the primary objective of any new process development. A review of the environmental problems of the copper industry indicates that the quest for a continuous smelting and converting furnace should be intensified.

Jan 1, 1983

By R. D. Brittain

In order to analyze and control the transport of harmful trace-element impurities in various smelting processes, it is necessary to have fundamental information about the chemical thermodynamic properties of the pertinent condensed and vapor phases. This paper describes recent thermodynamic studies of the gaseous arsenic sulfides and of the activity of arsenic in a copper-iron sulfide matte phase. These studies were carried out by high temperature mass spectrometry and by effusion vaporization techniques, which permitted clear identification of the molecular species involved, a decided advantage in such complex systems. The nature of the results obtained and comparisons with previous interpretations will be described.

Jan 1, 1983

By S. N. Sinha

The distribution coefficients of lead and silver between copper and matte phases have been measured at two different temperatures. Experiments covered the ranges of 0.009-1.8, 0.07-0.13, and 0-11 wt pct lead, silver, and iron in matte, respectively. The distribution coefficients of lead have been measured at 1405 and 1505 K and correlated with lead and iron concentrations in metallic copper and matte. The values of the distribution coef¬ficient of lead between copper and iron-free matte, at infinite dilution of lead, have been determined to be 3.60 and 4,06 at 1505 and 1405 K, respectively. The distribution coefficient of silver between copper and iron-free matte is independent of silver concentrations and has been measured to be 2.13 and 2.21 at 1400 and 1500 K, respectively. For an iron-bearing matte, the distribution coefficient of silver has been correlated with iron concentration in the matte at both 1400 and 1500 K. From the measured values of distribution coefficients, the Raoultian activity coefficients of PbS and AgS0.5 in copper-saturated matte have been calculated. At infinite dilution, the following equations correlating the Raoultian activity coeffici¬ents of PbS and AgS0.5 with matte- composition and temperature have been obtained: log Y° PbS =1.515 + 1080/T 0.14 NFes lbS Fog YAgS = -0.074 - 425/T + 0.09 NFes. - 0.5

Jan 1, 1983

By P. D. Nolan

Smelters operating under pollution control orders have become increasingly dependent upon the reliable operation of sulphuric acid plants and no factor affects the long term reliability of those plants more than efficient gas cleaning. The sources and characteristics of contaminants in smelter of fgases and the conventional approaches to removing these contaminants to accepted levels are discussed. New technology is described which offers advantages of lower capital cost, lower operating cost and reduced space requirements over the conventional approaches. This new technology has been developed by LAB s.a. and is licensed for metallurgical gas applications by Chemetics International Company.

Jan 1, 1983

By D. A. Robbins

The Resource Conservation and Recovery Act. of 1976 (RCRA) requires testing of waste materials as part of the determination of whether these materials are classified and managed as hazardous wastes. The adoption of one standard testing procedure and its application to all types of waste materials has stirred much controversy. In the center of this controversy is the appropriateness of this testing procedure in characterizing non-ferrous metal intermediates and slags. The authors have evaluated the relative availability of metals in several types of copper and lead slags as defined by various testing protocols. Also discussed is the relationship between the chemical character of the slag and the availability of metals to leaching and certain metallurgical practices that can influence metals availability.

Jan 1, 1983

By I. Barin

The thermodynamics of cyclone smelting of sulphidic copper ores is described using as example the production of copper matte with 75 wt % Cu. Equilibrium calcualtions and material and energy balances show that an increase in process temperature from 1600 K to 1900 K results in the extensive transfer of minor elements such as As, Sb, Bi, Pb, Zn,.... to the gas phase. A pilot plant for carrying out the cyclone smelting process is described. Calculations of material and heat transfer for the reaction of ZnS show that the smelting reactions of sulphides in the cyclone take place very rapidly at high temperatures. The dissociation of the sulphides with subsequent oxidation reactions in the gas phase plays an important part in. the process and is mainly controlled by heat transfer.

Jan 1, 1983

By R. M. Nadkarni

This paper examines the broad' economic parameters of copper smelting by conventional and new smelting technology. Location, transportation of products to market and pollution control options are discussed.

Jan 1, 1983

By C. M. Davidson

Contamination of by-product: sulfuric acid, by dissolved oxides of nitrogen ('nitrates') occurs under some operating conditions encountered in sulfide roasting and smelting,, notably when oxygen-enriched air is used. This 'nitrate' lowers the value of the acid and increases the effective cost of smelter gas desulfurization. The present paper describes measures taken at one smelter acid plant to remove this 'nitrate'; it discusses the mechanism by which 'nitrates' in some cases concentrate in one part of the plant and can be purged for more efficient treatment; and it describes a process developed by C-I-L Inc. for removal of 'nitrates' from such a purge stream. Advantages of the process include very low reagent cost, recovery of all sulfuric acid values and safe handling of nitrous fumes.

Jan 1, 1983

By Jan A. Aune

The paper describes a number of electric furnace equipment modules especially developed or modified for slag furnace applications. Both the resulting design concept for a modern electric sulfide smelter and some of the changes in traditional process-concepts made possible are outlined.

Jan 1, 1983

By G. Lindkvist

Roasting of concentrates with high impurity levels is normally done in multiple- hearth furnaces where the concentrates are heated with oilfired burners in order to remove As, Sb and Bi before the final sulfide oxidation. Although it is a countercurrent heat exchange process it uses a lot of oil. In order to develop an energy saving, and from a working environmental point of view a less harmful process than the multiplehearth process, pilot-plant tests have been done in a two-stage fluidized bed for partial roasting. The test materials have been As-rich concentrates with 8-25 % As some 5b and Bi. The Cu-content was 0-28 %. The tests have been successful with <0.3 % As,in the calcine and with an elimination of 5b between 80 and 90 %. In order to achieve the proper conditions for good impurity removal, 1.e. right temperature,residence time and sulphur potential, the tests were performed in a special designed roaster. The roaster consists of two beds with the facilities for recirculation of calcine, preheating of the blast, and possibility to use oxygen enrichment. The construction makes it easy to control the reactions that generate the heat in the bed and reduce the amount of dust that passes through the cyclones. As two roasting steps are used, the possibility to obtain optimal conditions for impurity removal is improved and the calcine can either be smelted to a normal matte, or after being dead-roasted in the second stage, be leached in the normal way for gold extraction. The calcine was smelted with slag. The matte and the slag obtained had low quantities of impurities in the matte and a favourable distribution of impurities to the slag.

Jan 1, 1983

By L. A. Harris

The formation of coke during coal liquefaction can eventually result in catastrophic failure of the conversion system. Coking typically proceeds by the formation of liquid crystals (mesophase) and the subsequent separation of these crystals from the plastic phase formed during heating of coal. The anisotropy of the mesophase makes it readily detectable in the optical microscope under polarized light. This study examines the solids formed during coal liquefaction processing by optical and electron microscopy. Observations on the relationships between the coke morphology, minerals and inert macerals are presented.

Jan 1, 1982

By Lawrence L. Brown

As part of the Federal effort to help maintain an adequate supply of fertilizer materials, the Bureau of Mines conducted research to characterize complex low-grade Michigan phosphate materials and to devise methods for recovering fertilizer-grade phosphate concentrates. The rock is from middle Precambrian sedimentary formations in the Marquette Range located in the central part of the Upper Peninsula of Michigan. Occurrence of phosphate-bearing sediments in Precambrian rocks is rare. This deposit, containing 12 to 15 pct P2O5 is believed to be the richest Precambrian phosphate deposit in the United States. Petrographic examination showed that the conglomeritic rock contains crystalline apatite both in "black pebbles" and in quartz matrix. Attrition scrubbing and sizing tests showed that there is no tendency for phosphate to concentrate in any of the sized fractions. In beneficiation tests, which included grinding to minus 325 mesh followed by phosphate mineral flotation using a fatty acid-fuel oil collector, a phosphate concentrate was obtained that had a grade of 30 pet P2O5 and a P2O5 recovery of 72 pct. This concentrate should be suitable for fertilizer manufacture.

Jan 1, 1982