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By Carla Lupi, Alessandro Pescetelli

"Spent lead battery recycling still shows few weak points in the achievement of a 100% recycling of different waste matters and by- products arising from the recycling process. Some of said problems are dealing with aqueous streams outgoing the recycling plant, and more particularly, a) the waste waters discarded from the breaking and separation unit, b) purification of the spent electrolyte drained from waste batteries and upgrade to a quality compatible with full re-use by the batteries’ manufacturers, c) purification of the mother liquors discarded in the sodium sulfate crystallization process so to produce a salt of commercial grade. All of the above listed problems have been satisfactorily overcome applying an electrochemical process that, through different process conditions and parameters, is able to remove the harmful impurities that hinder the successful commercialization of such by products, or, at least, that can avoid heavy and expensive treatment plant and operation.IntroductionAlmost 100% of commercial lead and lead alloys produced by secondary lead plants is recycled to the new lead accumulators manufacture. The other by-products and residues produced through the lead recycling process may be classified into two groups:a) matters reusable in the new accumulators production processb) matters produced as a result of various reagents and additives used in the recycling process, to be sold to different market sectorsQuality and saleability of by-products are significant points for the economics of the secondary lead plant operation, because, if said by-products are not saleable, they are just wastes, so offsetting potential revenues, and, at the same time, adding a heavy burden to operating cost, like disposal cost [1]. When looking at a typical, modern lead scrap batteries recovery cycle, it is quite evident that we are still rather far from dealing with a waste-less technology (fig.1).The group a) includes 3 by-products produced through the breaking process: among those matters the polypropylene only usually reaches a standard quality suitable for sale to lead manufacturing sector or to other sectors as well. The other two by-products, electrolyte and separators, do not still reach, through a viable and effective regeneration process, a quality standard sufficient for their re-use in the lead batteries sector ."

Jan 1, 2008

By Y. C. Avniel, T. E. Warner

"It is important to be able to measure sulphur and nitrogen in molten iron and steel on-line. Unfortunately, there are no solid electrolytes which are stable under oxidising conditions and in which the ions of these species are mobile. In this paper, novel applications of beta alumina electrolytes are described and the results compared with data in the literature. Excellent agreement was obtained confirming this approach as a viable method of detecting elements whose ions are not mobile in solid electrolytes.IntroductionIn the past two decades, the rate of many processes in steelmaking have increased substantially. The sophistication of chemical analysis has also increased but analytical equipment is frequently positioned a significant distance from the operating plant which dictates that time is spent taking a sample, sending it to the analytical facility, preparation of the analytical sample prior to insertion into the equipment. In many cases, the time taken for analysis can exceed the time taken for the actual process and is now the rate defining step. Furthermore, most analytical methods are unable to distinguish between the amount of element which is dissolved in the steel and that contained in precipitates. Even if the analytical equipment could separate these two, the distribution would have changed between the molten steel and the cast sample. It would be an advantage to analyse on-line for impurities in molten metals."

Jan 1, 1997

By Bo Zhou

During secondary aluminum recovery, complex aluminum scraps are melted and refined often in a rotary melting furnace and the aluminum metal has to pass through a molten salt layer and melt down in a bottom aluminum bath. Previous experimental study and industrial observations have indicated that salt shell formation and re-melting on the metal solids in the early stage plays a critical role in the overall melting process of the scrap. In the present paper, mathematical models are developed to simulate the process of salt shell formation and its re-melting, as well as aluminum melting in the molten melt. Influence of the salt layer properties, the residence time of the metal particles in the salt layer, the particle size, the temperature of bulk melt were investigated. Reasonable agreement with the measurement data was reached. The developed melting model will be used to construct a population balance model of the scrap melting behavior for a rotary melting furnace, taking into account the distributed characteristics of the scrap. Finally, an overall process model based on Computational Fluid Dynamics (CFD) for the rotary furnace will be constructed, coupling with the population balance model for the scrap melting.

Jan 1, 2003

By Krishna Parameswaran

This paper illustrates sustainability considerations in copper hydrometallurgy using examples of practices at ASARCO LLC, an integrated U.S. primary copper producer. Using the classic Brundtland Commission development of sustainable development, i.e., “development that meets the needs of the present without compromising the ability of future generations to meet their own needs,” the paper discusses how copper hydrometallurgical processes can be sustainable. The examples used to illustrate sustainable development and related concepts include: water conservation opportunities in milling and leaching operations; implementing green chemistry and promoting product stewardship in the electrorefining of copper.

By H. K. Lin

Thermodynamics of Cu-C1-H2O system and the kinetics of copper dissolution in cupric chloride solution were studied with emphasis on possible difficulties which may occur during copper electrowinning. E,-pC1 diagram of this system wasestablished. Equilibriumdistributionof various copper chloride complexes of different valent states at the presence of metallic copper was computed through the relations of the simultaneous equilibria. The mechanism-of copper dissolution in the cupric chloride solutions was proposed and the mechanism of copper electroposition was discussed. The researched results were used for guiding the investigation of copper electrowinning from cupric chloride solution.

Jan 1, 1991

By M. C. Ruiz

This work outlines the results of leaching studies on a copper concentrate containing chalcocite (Cu2S) and digenite (Cu9S5) with an acid saline solution of cupric chloride oxygenated at ambient pressure. The variables studied included the stirring speed, concentration of cupric ions, concentration of HCI, concentration of chloride ions, oxygen flow rate, temperature and time. The leaching system was found to be very effective for the dissolution of the concentrate. Over 95% of the copper was dissolved in 30 minutes with negligible dissolution of iron. The dissolution of copper increased with the stirring speed up to about 400 rpm and depended little on the total chloride concentration. The oxygen flow rate affected the dissolution of copper only below 0.1 1/min. The concentration of HC1 did not influence the dissolution providing its was sufficient to avoid the precipitation of copper oxychloride. The study of the effect of the temperature showed a maximum in copper dissolution around 90 "C

Jan 1, 1997

By Jennifer Murphy, Brad S. Schake, Karol Holmes, John R. FitzPatrick, Mike H. West

"The separation and purification of uranium from either nitric acid or hydrochloric acid media can be accomplished by using either solvent extraction or ion-exchange. Over the past two years at Los Alamos, emerging programs are focused on recapturing the expertise required to do limited, small-quantity processing of enriched uranium. During this period of time, we have been investigating ion-exchange as a method for extraction/purification of uranium from acidic media. In addition, waste stream polishing is associated with this effort in order to achieve more complete removal of the uranium prior to recycle of the acid. Extraction chromatography has been demonstrated to further polish the uranium from both nitric and hydrochloric acid media thus allowing for a more complete recovery of the actinide material and creation of less waste during the processing steps.We will discuss contact experiments for evaluation of eleven different resins for uranium removal from nitric acid, the evaluation (again by contact experiments) of uranium elution from the ion-exchange media by various chemicals, and small-scale experiments for the removal of 235U from nitric acid. Larger-scale (1 DO-gram) flow experiments, using depleted uranium, were done after the small-scale evaluation of the selected resin. A discussion is also included concerning the shortcomings of the contact experiments and how the flow experiments were modified in order to overcome these problems. We will also discuss the application of ion-exchange for some specific process needs at Los Alamos.Contact experiments were used to evaluate some commercially available solvent-impregnated resins in addition to evaluation of several resins of this type synthesized in our laboratory. These experiments involved both nitric and hydrochloric acid media. The data from these experiments will be used to determine the column size and amount of resin required to polish the waste stream produced by the ion-exchange process described above. Small-scale flow experiments will be described and data given on the mass balances achieved using this two step process.Future work for evaluation of new ion-exchange and solvent-impregnated resins as well as the search for new eluants will be discussed. Other future experiments for both processes, including large-scale experiments, will be discussed in detail."

Jan 1, 1996

By Sergio Sanchez-Segado, Yuan Zhang, Animesh Jha, Ahmad Fahmi Ruzaidi

Niobium and tantalum are considered critical materials because the increasing demand in the energy sector which is reliant on limited abundance of these two metals in minerals. Traditionally, niobium and tantalum mineralsare digested using hydrofluoric acid at moderate temperatures, producing oxy-fluorides which are separated by solvent extraction, involving the use ofhazardous chemicals. The increasing environmental pressures are forcing the industry to search for alternative low carbon processing methods. In this paper alkali roasting based separation and beneficiation, which is not well understood in the literature, is proposed, for which the kinetics and thermodynamic equilibria for the formation of sodium tantalate and niobate with sodium hydroxide are analyzedat the temperature range of 400ºC to 700ºC. The apparent activation energy of formation,changes from 31.0±0.8 to 22.3±1.2 kJ mol-1 and from 23.8±1.2 to110.2±12.8 kJ mol-1, for tantalate and niobate, respectively. The reaction mechanism is examined on the basis of the analysis of reaction products using X-ray powder diffraction (XRPD) and X-ray fluorescence (XRF).

Jan 1, 2015

By Brian R. Green

Resin-in-pulp (RIP) technology has been developed for recovery of gold. It is now time to look forward to the potential for application of the technology to other situations. Some cases have been identified and have merited preliminary testwork. Four examples, which illustrate the potential of RIP, are dealt with in this paper. These include removal of metal-cyanides from pulps, recovery of manganese that is difficult to wash from filter cakes, recovery of nickel from low grade pulps, and recovery of zinc from process residues. The discussion includes descriptions of the problems, factors that affect the choice of resin, and factors that will affect the economics of the process.

Jan 1, 1998

By Mark William Kennedy

Modern metallurgical plants typically have complex flowsheets and operate on a continuous basis. Real time interactions within such processes can be complex and the impacts of streams such as recycles on process efficiency and stability can be highly unexpected prior to actual operation. Current desktop computing power, combined with state-of-the-art flowsheet simulation software like Metsim, allow for thorough analysis of designs to explore the interaction between operating rate, heat and mass balances and in particular the potential negative impact of recycles. Using plant information systems, it is possible to combine real plant data with simple steady state models, using dynamic data exchange links to allow for near real time de-bottlenecking of operations. Accurate analytical results can also be combined with detailed unit operations models to allow for feed-forward model-based-control. This paper will explore some examples of the application of Metsim to real world engineering and plant operational issues.

Jan 1, 2014

By Batric Pesic

Dissolution of gold with sodium bromate solutions of various compositions was studied by using a rotating disc technique. The role of bromide ion, acid and externally added bromine was examined. It was found that sodium bromate could not dissolve gold in the absence of either acid or bromide ion, or both. When acid was absent, no bromine necessary for gold dissolution could be produced. When bromide ion was absent, formation of soluble gold bromide species, AuBr,-, was not possible. Bromate concentration had a complex effect, and it was dependant on bromide ion concentration. For fixed initial bromide ion concentration, gold dissolution rate increased with sodium bramate concentration increase until certain level, beyond which further increase of bromate concentration decreased the gold dissolution rate. The negative effect of bromate was explained by the depletion of necessary bromide ion. Sulfuric acid concentration effect was a function of initially present bromine.

Jan 1, 1992

By John Anawati

Bauxite residue is an environmentally unfriendly byproduct of alumina manufacturing, produced worldwide in large quantities. This material contains 50– 100 ppm of scandium, a critical material for the production of stronger, weldable, corrosion resistant, and heat tolerant aluminum products. Aircraft manufacturers are particularly interested in Al–Sc alloys because of its ability to form weldable alloys that could potentially reduce aircraft weight by 15–20%. Because of its abundance and low cost, bauxite residue has the potential to be used as an efficient feedstock for valorization processes to recover its scandium content, while in turn degrading this problematic waste. In this project, we developed an efficient process to recover scandium and rare earth elements from a Canadian bauxite residue with high extraction yields, using industrially scalable and economical techniques. The process employs a modified version of sulfuric acid leaching and subsequent impurity removal by selective precipitation. This article outlines the current progress and design rationale in the development and optimization of this innovative and sustainable recovery process.

By Mikio Kobayashi

Extraction of valuable metals from sulfide ores continues to be a very important, process and so the strict control of discharge of harmful metals in effluents from refineries becomes more important in the future. The recovery methods for heavy metals have been developed. Some metals such as Se and As are still difficult to be removed to very low concentration, although the techniques for recovery and removal for many kinds of heavy metals have already been developed. Especially, in case of Se the recovery system from water with low concentration has not be developed yet, although the WHO decided Se to be harmful for human beings and then the discharge control is under obligation now. In general Se exists as selenite ion and/or selenate ion in aqueous phase and selenite ion is able to be recovered by coprecipitation with ferric hydroxide or by reduction to solid selenium by general reductants. Selenate ion, however, has a strong resistance to conventional treatments. Therefore the new technique for the recovery of Se from water including selenate ion has to be developed. In this presentation the new approach for removal of selenate ion using the reaction in which ferrous ion is oxidized to ferric ion is presented. Selenate ion is reduced to selenite ion during the reaction and then to solid selenium, while ferrous ion is oxidized to ferric ion. The coexistence of activated carbon is very useful to increase the reaction rate. The use of iron powder is also effective and very useful for reducing gel-like precipitates mainly consisted of ferric hydroxide. The concentration of the residual selenate ion is probably under 0.1 ppm after recovering Se by the mentioned-above approach. In addition to the mechanisms of these reactions, the effects of pH, coexistent positive and negative ions, and reaction temperature are also presented. Furthermore the investigation of the behavior of selenosulfate is presented.

Jan 1, 1998

By Bingliang Gao, Junli Xu, Michal Korenko, Jinzhao Guan, Liangxing Li, Zhongning Shi, Zhaowen Wang, Aimin Liu

Al-Si alloy, a precursor of solar grade silicon, was prepared by direct electrolysis in cryolite molten salt at 950 oC using high purity silica as material, liquid aluminum as the cathode and high purity graphite as the anode. The electrochemical behavior of Si(IV) ion was investigated using cyclic voltammetry method. The electrolysis products were characterized by XRD, SEM/EDS and ICP. The results indicate that the reduction process of Si(IV) on tungsten electrode is a two-step process and there is about 0.6 V gap between the two steps. The contents of boron and phosphorus in the aluminum-silicon alloy are 3 ppmw and 8 ppmw, which will make the directional solidification purification effectively and reduce the cost of preparation solar grade silicon from metallurgical grade silicon.

Jan 1, 2015

By Gökhan Demirci, Ishak Karakaya

"Energy consumption in electrolytic magnesium cells is well above the theoretical values. However, the mechanism of the back reaction, the main cause of the current losses, has not been fully understood yet. Magnesium dissolution into the melt is generally regarded as the limiting step for the back reaction. Accordingly, present cell designs are made with priority given to fast magnesium removal from the cell. However, experimental data and modeling results in this study indicate that the limiting step for the back reaction between magnesium and chlorine is the chlorine dissolution into the electrolyte when physical contact between electrolysis products was eliminated. Effects of chlorine bubbles on the current efficiency and the cell potential were investigated. Results show that the extent of back reaction is proportional to the chlorine surface area in contact with the electrolyte per unit time, and the cell potential increases with the amount of chlorine bubbles inside the electrolyte.1. IntroductionMagnesium is less dense than the electrolyte in electrolytic magnesium production. Therefore, both electrode products, magnesium and the chlorine gas, move upwards inside the molten salt electrolyte during electrolysis. The upward motion of electrode products promotes the most important current loss mechanism, the ""back reaction"". Separation of the highly reactive species; liquid magnesium and the chlorine gas in the cell, to prevent their recombination is one of the main concerns in cell designs. The employment of large inter-electrode distance or a separation wall in early cell designs; decreased the extent of recombination, but increased the cell voltage and energy consumption. Recent cell designs, on the other hand, make use of lifting action of chlorine gas [1,2] by utilizing smaller inter electrode distances to separate the magnesium and chlorine gas faster. Although energy consumption was reduced, but more physical interactions between electrode products make electrolytic magnesium cells still highly inefficient when energy consumptions are compared with the theoretical values. Today, the most efficient industrial cells utilizing high purity feed operate at 10.5-11.5 kWh kg-1 Mg [3-5] and it is considerably higher than the theoretically attainable value of about 6.0 kWh kg-1 [6]. This large gap demonstrates the necessity of more research on physics and chemistry of magnesium cell electrolysis."

Jan 1, 2011

By Guozhu Ye

"One of the most essential problems associated with the treatment of EAF dust is its high content of halogens. For most thermal processes for zinc recovery, such as the plasma processes with a zinc condenser, the halides in the gas stream will form a dross phase that results in a low zinc yield. For those with zinc oxide as main product, such as Waelz oxides, the high halogen content in the product implies a great degradation of the product quality and the product can only be sold at a low price. Further processing of zinc oxide with high halogen content either by pyrometallurgical or hydrometallurgical processes will also result in process problems.This paper will review the pre- and post-treatment alternatives for halogen removal based on the comprehensive characterization work that has been carried out at MEFOS and the preliminary experimental results.The experimental results show that chlorine and fluorine content could be reduced to 450 ppm and 50 ppm respectively by selective sulfation, and to about 200 ppm by soda leaching. Selective sulfation of zinc oxide in the EAF dust will also be discussed."

Jan 1, 2000

By Donna M. Noel

Bacterial strains have been cultivated from solids previously exposed to cyanide that will tolerate 300 ppm sodium cyanide under anaerobic conditions. In selected solid samples, these bacteria have been shown to reduce the level of cyanide from approximately 300 ppm to essentially zero in about 50 days under anaerobic conditions. Various media were investigated, and the nutrients providing maximal growth were ?established .. Degradation of cyanide in sterilized solids was determined for comparison with degradation obtained in bioactive solids. All experiments were conducted at ambient temperature and initial pH of approximately 10.5.

Jan 1, 1991

By Feng Gao

A general unsteady- state model, based on a cracked substrate, has been developed to account for reaction and diffusion within porous substrate during oxidation of Carbon Fiber Reinforced Carbon matrix (CIC) composites. The effects of several parameters, such as diffusion and reaction rate ratio, oxygen concentration, and composite density, on oxidation process are explored. Also, theoretical results for a set of parameter values of the CIC composites are compared with experimental data. It shows that the model predicted values agreed well with the experimental data in weight loss. Based on this model, quantitative predictions of oxidation of a composite with cracked substrate can be made.

Jan 1, 1993

By Patrick R. Taylor

Iron phosphate glasses are promising host matrices for vitrifying actinide rich nuclear wastes materials because of their high solubility of actinide oxides, high chemical durability, and relatively low melting temperatures. An iron phosphate waste form was developed at the University of Missouri-Rolla. The structure and property of the waste form were well characterized by materials techniques. However, to scale the process and advance it to commercial viability, it is necessary to understand the processing parameters, such as the partitioning of waste elements and the viscosity as a function of temperature. Viscosity of 40 Fe203 - 60 P205 mole % iron phosphate melts (prepared with phosphorous pentoxide and ferric oxide) at 1000-1200 C was measured by the rotating-spindle method. It was discovered that this fluid has non-Newtonian behavior. Experiments were performed to study flow properties following the Standard Test methods for Rheological Properties of Non-Newtonian Materials by Rotational (Brookfield) Viscometer (ASTM D 2196-86). Samples prepared using ammonium phosphate and ferric oxide showed Newtonian behavior and the temperature dependence of the viscosity was studied over the range of 1000 to 1200 degrees C. The difference in flow behavior between the two fluids was analyzed in terms of preparation conditions and variation in the final composition and phases. The partitioning behavior of waste elements in the iron phosphate glass was studied by melting in a high temperature furnace and JCP analysis. The experimental results show that the solubility of Ce and Sr in phosphate glasses is significantly higher than the solubility associated with borosilicate glasses. This strengthens the conclusion that iron phosphate may be a viable alternative to borosilicate glass for immobilization of high heavy-metal-content wastes and actinide rich wastes.

Jan 1, 2002

By Xueming Lv

The rotary kiln-electric furnace (RKEF) process is the main method for producing ferronickel from nickel laterite ore. However, this process is energy intensive as it involves several high temperature steps. Therefore, a novel process is proposed to directly produce ferronickel from nickel laterite ore by semi-molten reduction, which is expected to be realized in a rotary hearth furnace (RHF). The RHF process is able to shorten the flow sheet, decrease the reaction temperature as well as reduce energy consumption. In this study, the influence of basicity on reduction of nickel laterite ore was investigated. The results showed that it is possible to produce the ferronickel nugget directly at 1400 °C when the quaternary basicity [(mCaO + mMgO)/(mSiO2 + mAl2O3)] was fixed at 0.60. Under this experimental condition, the grade and the recovery ratio of nickel reached 11.53% and 98.59%, and the grade and recovery ratio of Fe were 84.16% and 68.72%, respectively.