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By Sheng Dai, Yuan Lee, Haiming Xiao, J. P. Young

"There are numerous analytical applications of scatter-emission and/or absorption spectroscopy applied to liquids and solids in the temperature range of 0 to 350°C. In this paper an all-silica fiberoptic probe is described which is useful for spectral analyses from 0 to 1600 K and can be used in harsh chemical environments. The probe has been used for Raman spectral analyses of many molten salt and solid material systems to 1000°C. It has applications for such studies at higher temperature ranges. The instrumentation required along with the demonstrated and proposed applications of the all-silica probe are presented and discussed.IntroductionThere are many kinds of scatter-emission spectroscopies that are of value for analytical measurements. Fluorescence, reflectance, arc or spark emission are descriptors for some of these. Raman scatter spectroscopy is also quite a useful technique for analytical measurements.In Figure 1, we give a simplified explanation of the Raman effect. If one shines monochromatic light into a sample, light may be absorbed, exciting the sample to some virtual state. We know from experience that almost all of the light is re-emitted in the same wavelength range. This is called Rayleigh or Mei scattering and is designated in the figure by the arrows in both examples that point up and down from the same lower energy state. A very small percentage (the order of 10-4%) of the monochromatic light is re-emitted leaving the sample at a vibrationally-excited state. Thus, this light is at a distinctly lower energy compared to the exciting radiation. This is called a Stokes shift and is represented in the left-hand example by an arrow descending to a more energetic vibrational state. If the sample is not at a temperature of absolute zero, some of this vibrationally excited state will be thermally populated. That portion of the sample still absorbs and re-emits exciting radiation as Rayleigh scattered light, but a small percentage of the exciting light is re-emitted as the sample relaxes to the lower vibrational state. The energy of this light is of higher energy and is called an anti-Stokes shift, depicted in the example to the right. Notice that the energy separation of the Stokes or anti-Stokes shifted emission from that of the exciting radiation is the same, and expressed in ~cm-I. The intensity of either shifted emission is a function of the population of the vibrational energy states; therefore, the ratio of the intensity of Stokes to anti-Stokes signal varies with absolute temperature. We will come back to this point later."

Jan 1, 1997

By Yan Wen

For the impurities in the copper smelting waste acid, SO3, Cu, As, Pb, Zn, Re and other elements enter the waste acid and generate a lot of arsenic residue, gypsum and neutralized residue, in which Cu, Zn and Re metals have not been recycled. Cu, Re and As are separated by step-wise vulcanization. The valuable metals of Cu, Zn and Re are recovered by separating zinc through pH adjustment. Calcium injection is conducted for boiler for reducing the amount of SO3. The residues generated in the form of arsenate and hydroxide will be returned together with arsenic filter cake for smelting treatment so as to achieve the purpose of valuable metal recycling and solid waste reduction and harmless treatment.

By Jerome P. Downey

In the thermal treatment of electric arc furnace (EAF) dusts, zinc is reduced, volatilized, and ultimately recovered either as liquid metal in a splash condenser or as solid zinc oxide in bag filters. During the process, the duet's chlorine and fluorine content also enters the gas phase and condenses as dross in the splash condenser or as salts which contaminate the zinc oxide product. Pretreatment of EAF dust by pyrohydrolysis appeared to offer a means of minimizing the duet's halogen content. The primary research objectives were to experimentally verify the technical viability of pyrohydrolysis and delineate the process parameters requisite for efficient halogen removal. To this end, representative EAF duet samples were secured and characterized by x-ray diffraction, scanning electron microscopy, and Mössbauer analyses. Specific- experimentation focused on the response of halogen extraction to variations in temperature, retention time, water vapor partial pressure, and various additives. The experimental results proved that 97 to 99 percent chlorine extraction and 80 to 85 percent fluorine extraction are consistently achieved when EAF dusts are blended with silica and roasted at temperatures of 850°C or greater in a furnace atmosphere of 75% steam (diluted by air). A statistical analysis further established that more than- a single optimal point exists, thus affording flexibility in parameter selection (e.g., by increasing temperature, the necessary retention time and additive concentrations are decreased). The findings substantiate the feasibility of pyrohydrolysis roasting in reducing the chlorine and fluorine in the EAF dust to a level that will obviate industrial concerns about halogen contamination. The end-product of the pyrohydrolysis procedure is a de-halogenated, self-fluxing calcine which can be directly charged to a plasma or flame reactor. The paper includes design parameters and flow diagrams illustrating the pyrohydrolysis process integrated with the plasma and flame reactor technologies.

Jan 1, 1992

By Zhonglin Ye, Yifeng Shi

"This paper has outlined forms of Au & Ag losses in copper smelting process and methods for increasing Au & Ag recovery, analyzed factors influencing Au & Ag recovery in copper converting process, presented Au & Ag behavior in copper electrorefining process, and reviewed effect of current density/electrolyte circulation rate during electrolysis and surface finish of cathode on Au & Ag losses. Measures and research direction for decreasing Au & Ag losses in electrolysis have also been introduced. Based on Au & Ag behavior in copper electrorefining process and previous studies by others, new approach for increasing Au & Ag recovery in copper smelter has been discussed. And brief comparison has made between continued multiplication method and equilibrium method application in the case of calculation of Au & Ag recovery in copper smelter.IntroductionAs gold and silver are the major by-products from copper smelting process, efficient Au & Ag recovery has become one of the key approaches for copper producers to increase economic efficiency. With similar physicochemical properties, Cu, Au and Ag belong to the first subgroup of elements in the same periodic table. Au and Ag will be enriched into Cu phase firstly when both matte-slag phase and copper-matte phase appear in copper smelting process. However, great changes have taken place in Au & Ag proportions into individual phase due to changes of physicochemical conditions in each smelting process. Metallurgists at home and abroad have carried out a great deal of pilot plant tests and laboratory tests in order to increase Au & Ag the former Soviet Union with regard to Au & Ag losses in copper smelting process in the 1970s and 1980s, and he proposed solutions to increase Au & Ag recovery in copper metallurgical plants. As more than 20 years passed, Jingchun Lu's paper, Discussion on Increasing Au & Ag Recovery in Copper Smelting System, remains as a literature of the most comprehensive study. Based on Jingchun Lu's literature, the authors of this paper discussed new approaches to increase Au & Ag recovery in copper metallurgical plants with combination of many researches done by other researchers for over 20 years."

Jan 1, 2013

By Dan Wang, Yuanbo Zhang, Guihong Han, Guanghui Li, Tao Jiang, Yanfang Huang

"Hematite concentrates are characterized by bad high-temperature reactivity and poor balling index, which restrict their large-scale application in the production of oxidized pellets. An organic additive, namely MHA, was authorized and used as binder recently in China. Compared with bentonite, the effects of MHA on compressive strength of hematite pellets at various firing conditions were investigated in this study. Experimental results showed the compressive strengths of preheated pellets with different binders were increased with increasing the preheating temperature and time. The compressive strength of preheated pellets with MHA binder was lower than that of pellets with bentonite, which can be ascribed to the high porosity of pellets with MHA binder. However, the compressive strength of roasted pellets with MHA binder was higher than that of pellets with bentonite. The compressive strength of finished pellets balled with MHA binder 1.0 wt% could meet the operation requirements of grate-kiln process.IntroductionHematite concentrates are characterized by bad high-temperature reactivity and poor balling index, which can lead to the appearance of those problems with increasing the energy consumption, shortening the useful life of equipment, and finally increasing the operation cost of oxidized pellets plants [1-2]. Some investigations have been conducted based on improving the pelletizing technique of hematite concentrates, such as pretreatment of raw materials [3-7], optimization of ore proportioning [8], addition of solid fuels [9-16], and so on. Employing high pressure grinding roller for the treatment of hematite concentrates revealed that the mechanical strength of wet green pellets could be improved. However, the mechanical strength of fired pellets was not improved obviously [7]. Huang, et al., pointed out that the preheating and roasting temperature may be decreased and the compressive strength of fired pellets could be increased by blending a certain proportion of magnetite concentrates with hematite [8]. Nevertheless, there are a variety of magnetite ores different in physical and chemical properties in China, resulting in the instability operation [17]."

Jan 1, 2012

By Federico Chavez

The process for recovering lead from battery residues used in several Mexican Plants include lead blast furnace and rotary furnaces. The formers are basically fed with recycled batteries together with the necessary additives to produce metallic lead. One of the by-products generated in the blast furnace is a dust mainly formed by lead sulfide. The rotary furnace is used to recover lead .from lead batteries, dross from the refining-alloying process and the leady fines produced in the blast furnace. This paper describes thennodynamic analysis made to the rotary furnace process to understand the effect that each component of the system has upon the lead recovery. In order to enhance the process, the influence of iron chips composition and excess coke on slag viscosity is discussed. A computer optimization program . has been developed to design the furnace charge based on material and energy balances, .together with the thennodynamic equilibrium calculation.

Jan 1, 1995

By Stig Petersson

Slag from the converting of copper matte is usually recirculated to the smelting furnace. This recirculation generally causes disadvantages as magnetite-build-up in the furnace, accumalation of impurities as antimony, lead, nickel etc in the process. The treatment of converter slag in a separate furnace in order to recover the copper and nickel content would be of advantage from several points of view. At the Mining and Metals Division, Boliden, testwork has been carried out to treat converter slag from the PS-converters in a separate furnace. The tests have been performed in laboratory and pilot plant scale. The pilot plant tests have been carried out in a TBRC with charges of 5 tons. Based on these tests a full scale TBRC has been projected in order to treat the slag from the PS-converters. This slag will be reduced with copper concentrates to give a matte and a final slag low in copper and nickel. The background and data from the testwork are presented. Also the lay out, technical data and flowsheets for the projected process are shown as well as some production data from the Rönnskär smelter.

Jan 1, 1976

By Filiz Sahin

This paper presents a synthesis of TiB2 via carbothermal reduction method using a mixture of TiO2, B4C and C prepared in molar ratio of 2:1:3. Reduction experiments were carried out in a high temperature graphite furnace in a graphite crucible under argon atmosphere at different time (0, 15, 30 and 60 min.) and temperatures (1400, 1500 and 1600 °C). The products obtained were investigated using XRD technique.

Jan 1, 2008

By Miao Tian

Large quantities of copper complex resources are produced globally and urgent to be cleanly processed. This article presents a thermodynamic analysis of mixed smelting process including low-grade polymetallic copper sulfide concentrates, high copper content sulfide concentrates, metallurgical by-products (copper removal slag from lead metallurgy), and copper powder from electronic waste. A top blown smelting reactor to simulate mixed smelting process is developed using a metallurgical process simulator, METSIM. Reactor parameters, heat loss and phase distributions are estimated from actual plant data. The proper proportion between complicated primary and secondary copper resources is determined by analyzing the influence of the feed rates of various resources, oxygen, silica flux and revert on the smelting performance. Autogenous smelting process is built by optimized matching materials of copper complex resources, in terms of the reactor temperature, copper content in matte and slag, and the percentage of magnetite in slag.

By L. W. Beckstead

In a conventional zinc refinery plant, zinc concentrates were roasted at 950°C. The calcine was ground and leached in a series of leaching vessels using sulfuric acid. The pH in the first leaching vessel was maintained at 2.5, while the pH of the solution exiting the last vessel was about 5.4. The leached residue typically contained (in percent) 0.1 Ag, 0.2 As, 0.7 Cd, 2 Cu, 15 Fe, 10 Pb, and 15 Zn, and it was classified as hazardous material according to the EP-toxicity test. In order to make the residue non-hazardous, and to recover most of the metal values from the residue, a brine leach process was developed. The process consisted of leaching the zinc leach residue in CaCI, brine solution at pH 2 for 1 hour at 90°C. Silver extraction was about 95 percent, while lead, copper, cadmium, zinc, and iron extractions were about 80, 50, 50, 30, and less than 0.5 percent, respectively. More extreme conditions of acidity could have been used in the leaching stage to increase zinc dissolution, but iron dissolution would have significantly increased which would have complicated subsequent recovery steps. The leached and washed residue passed the EP-toxicity leach test and could be disposed as non-hazardous. Silver, copper, and lead in the leach solution were recovered by zinc cementation, while zinc and cadmium were recovered by sulfide precipitation. The resulting solution can be recycled in the process after magnesium precipitation.

Jan 1, 1993

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 R. C. Hubli

A panial equilibrium model? to simulate the dissolution of millerite (NiS) in aqueous solutions containing copper(II) chloride as the oxidizing species has been developed. The predominant copper(I) and copper(II) species are CuQ3 and CUO2 respectively. The model computes the initial concentrations of the species present in the aqueous phase under the specified input conditions, prior to the simulation of dissolution. During the dissolution of millerite, nickel enters the leach liquor as NiH and it has been found that the H+ decreases as a function of NiS dissolution. The simulation has been accomplished under conditions prevailing during actual dissolution, with only one mineral undergoing dissolution. The model can be applied for the simulation of co-dissolution of two or more sulfides. Under the given conditions, the precipitation of Cu1(OH»)O is negligible but loss of Cu(1l) could be significant if the initial H+ is lower than 0.03 M. The results of the simulation compare favorably with experimental observations.

Jan 1, 1996

By Jose Castro

The growing demand of scrap to supply the electric arc furnace has driven to search for new alternatives of raw material. The DRI produced using self-reducing pellets has become competitive due to the potential use of a wide range of carbonaceous materials such as coal, charcoal, biomass etc. In this context, the rotary kiln process using improved technologies such as post-combustion and self-reducing burden is a promising source of high quality raw materials. This paper presents a mathematical model of the rotary kiln process designed for self-reducing pellets and post-combustion. The model is based on the transport equation of two-phase flow, energy and mass transfer. The solid material is composed of a typical self-reducing pellet. The model considers the solid phase (C, volatiles, Fe2O3, Fe3O4, FeO, Fe, H2O, SiO2, Al2O3, MgO, P2O5, K2O, Na2O, FeS, CaO and gangue) and the gas phase (N2, O2, CO, CO2, H2, H2O, SO, SO2 and SiO). For each of the above components a conservation equation is solved and the mass and energy transport is accounted. The set of differential equations are coupled by the rate equations describing the kinetics of the several reactions, which take place within the rotary kiln. All the conservation equations are solved based on the finite volume method applied for a three-dimensional cylindrical coordinate system. Simulation results are presented for global parameters such as metallization degree, productivity, gas utilization ratio and calorific value. Inner conditions such as three-dimensional gas and solid temperature patter and compositions are discussed.

Jan 1, 2006

By I. D. Reznik

Regularities of cobalt and nickel distribution between slag and matte, slag and metallic alloy on the base of concepts on exchange reaction equilibrium are considered. It is shown that the distribution of cobalt and nickel in industrial processes approaches to equilibrium one. Oxysulphiae influence on the bahaviour of cobalt, nickel and sulphur is shown. The recommendations on conduction of the processes of smelting, converting and slag cleaning based on the analysis of the methods or" non : ferrous metal separation from iron are given.

Jan 1, 1993

By Xu Zhang, Xuewei Lv, Guibao Qiu

Slag foaming phenomenon is of vital importance to the mass and energy transfer in metallurgical processes. A considerable extensively studies carried out via out-gas in the past cannot simulate well the foaming phenomenon formed in the blast furnace where high TiO2 iron ore is used. A gas reaction was designed in the water-glycerol system to simulate the inner-gas system. This study investigated the influences of solution viscosity, particle concentration and particle size on foaming caused by endogenetic gas. The results show that the foaming height decreases with the increase of solution viscosity, which means reduced foaming ability, more difficult foaming elimination process and prolonged time for natural defoaming. With increasing the solid particle content, the foam height presents a trend which increases firstly and then decreases. Under a certain solid particle content, foaming height decreases with the increase of solid particle size, indicating a weak foaming ability.

Jan 1, 2015

By Guo Xueyi

The dissolution behaviors of valuable metals, lead and zinc, from secondary fly ash generated in municipal incineration plants were investigated using some lixiviants: sulfuric and hydrochloric acids, acetic acid and some chelating reagents including L-asparaginic-N,N-diacetic acid (ASDA), a biodegradable, and therefore, environmentally benign novel chelating reagent. It was found that zinc exists mainly as ZnO, whereas Pb probably as PbOHCI and PbO, and the easily soluble components in SFA are KCI and NaCl. Suitable amount of HCI can dissolve all of lead and zinc from SFA. Sulfuric acid can selectively extract zinc leaving lead in the residue. Ethylenediaminetetraacetic acid (EDTA) is an effective chelating reagent to extract both zinc and lead. Although ASDA and diethylene¬triaminepentaacetic acid (DTPA) can selectively extract more than half of lead from SFA, it would by no means be regarded as highly effective reagents for the extraction of these metal values. Keywords: Lead, Zinc, Secondary fly ash, Leaching, Dissolution

Jan 1, 2002

By Baozhong Ma, Yonglu Zhang, Yongqiang Yang, Chengyan Wang, Yongqiang Chen

During the past decades, slurry electrolysis (SE) has been implemented commercially for the processing of bismuthinite and complex Pb-Cu bearing gold concentrates. Recently, SE was proven effective for the treatment of As-rich antimonic gold concentrates. Laboratory test results suggest over 98% of the antimony was extracted, while the extraction of arsenic and gold was less than 0.5%, and that of iron was less than 6%. Moreover, the cathode antimony contained over 98% antimony and less than 0.3% arsenic. Considering the disadvantages of traditional 3 kA slurry electrolysis baths, such as smaller electrode area, reduced capacity, and greater electrode deterioration, the authors have developed an innovative 12 kA slurry electrolysis bath equipped with mesh and fence type titanium alloy electrodes. Furthermore, the technique was successfully used within a pilot scale plant yielding results similar to those observed in the laboratory. The technique yielded ametallic antimony ingot of 99.9% purity after arsenic removal via the addition of Na2CO3.

Jan 1, 2014

By Florian Kongoli

Converters have been playing an important role in the extraction and processing of metals ever since the first type of converter was invented about 100 years ago. Historically their operation has been mainly based on the experience of talented operators rather than on strict control and optimization technologies. However, in the new realities of unavoidable necessity to increase productivity and in the conditions of diversification of primary materials from various geographical areas, improving control and optimization techniques have become indispensable. In this paper a review of the authors? previous work in terms of improving control and optimization of converter operational practices related to magnetite content and precipitation, slag and metal blows, problematic and dangerous elements such as As, Sb etc. has been described by highlighting the advantages that the new control and optimization methods and tools bring to everyday converter practices. Several examples are given and future work is underlined

Jan 1, 2005

By Valery Kaplan

Sulfur emission in the form of SO2 in flue gases is one of the most serious atmospheric pollutants associated with coal combustion and non-ferrous metals production. The carbonate eutectic method for removing SO2 from flue gases at 723–923 K was initially proposed in the 1970s but despite its great efficiency (SO2 concentration in the flue gas after purification reached 0.003 volume %), it could not be implemented by industry due to the complexity of the carbonate melt regeneration stage. Earlier we proposed a method suited to coal-firing power stations where the melt was regenerated using CO as a reducing agent. However, most metallurgical plants do not use coal and therefore lack a large source of CO. Here we propose a method for removing sulfur from the carbonate eutectic melt by purging it with natural gas or a natural gas/air mixture, which are available in the vast majority of metallurgical plants. This reaction leads to the reduction of sulfate to H2S gas that leaves the melt. The experiments we conducted show that nearly complete sulfur removal from the melt is possible at 823 K and that the reaction rate is sufficiently high for a large scale process. One can foresee that this carbonate melt-based SO2 removal technique may become a practical and economically attractive method for limiting sulfur emission to the atmosphere from non-ferrous metallurgical processing plants.

By M. S. Moats

Galvanic stripping, in conjunction with solvent extraction, has been proposed as a technical option to the challenging problem of iron removal in certain hydrometallurgical processes. The galvanic stripping process is based on the ability of a solid metal to directly reduce ferric ion to the ferrous state in an organic media. Stripping the iron into the aqueous phase is then easily accomplished. Previous work has shown the reaction kinetics and efficiency are affected by such operating parameters as water and oxygen contents, temperature, time and metal reductant. In this study, the optimum operating range for some of these variables was determined. Both zinc and iron metal were used in the separate stripping of iron from D2EHP A. Reasons for the differences in the extent of the reaction obtained using the various conditions are discussed.

Jan 1, 1996