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By Michal Rzyman, Nakamura Takashi, Shibata Etsuro, Grabda Mariusz, Oleszek-Kudlak Sylwia

"Thermodynamic considerations indicate that heavy metal oxides should easily react with HBr, the main gaseous product from the thermal decomposition of tetrabromobisphenol A (TBBPA), forming low boiling point metallic bromides suitable for volatile separation. Mechanisms and kinetics of the bromination reactions must be well recognized prior to developing of a new treatment for the simultaneous recycling of plastic waste containing brominated flame retardants (BFRs) and metal oxides (printed circuit boards, automotive shredder residue, plating sludge, metallurgical dusts). In this work, a differential scanning calorimeter and laboratory-scale furnace were used to investigate the possibility and conditions of the bromination of ZnO by product of thermal decomposition of TBBPA. The formed solid, condensed and gaseous products were analyzed by X-ray diffraction analysis, electron probe microanalysis, inductively coupled plasma analysis, ion chromatography and gas chromatography coupled with mass spectrometry. Introduction Tetrabromobisphenol A (TBBPA) is the largest volume brominated flame retardant (BFR) in production today and is used in more than 70% of the world’s electronic and electric (E&E) appliances [1]. The growth in the production of E&E products and the fact they become obsolete so quickly cause significant problems in the safe disposal and recycling of the electrical and electric waste (E-waste) and other BFR-containing waste [2]. Among various treatment processes, thermal methods are most useful since they allow the recycling and recovery of both the organic and inorganic fractions of the waste. However, incineration of the BFR-containing wastes results in the emission of hazardous organobromine compounds, while the main portion of bromine released from decomposed BFRs is present in flue gas as hydrogen bromide (HBr) [3]. HBr, which is known to damage incineration systems, seems to be a very effective bromination agent for many metallic oxides present in waste. The concept of this study is to take advantage this of its property."

Jan 1, 2008

By Pertti Koukkari, Nagendra Tripathi, Karri Penttilä, Justin Salmine

ChemSheet is a thermodynamic multi‐phase multi‐component simulation software, which is used as an Add‐in in Microsoft Excel. In ChemSheet, the unique Constrained Gibbs free energy method can be used to include dynamic constraints and reaction rates of kinetically slow reactions, yet retaining full consistency of the multiphase thermodynamic model. With appropriate data, ChemSheet models can be used to simulate reactors and processes in all fields of thermochemistry. The presentation will cover off‐line modeling of Cu‐flash smelters and advanced thermochemical simulation coupled with on‐line process control of Cu‐Ni smelting. The presentation will describe an off‐line model of Cu‐smelter based on critically assessed properties of the Al-Ca-Cu-Fe-O-S-Si –system (slag, matte and liquid metal) by using the quasichemical model. A four‐stage reactor model (shaft, settler, uptake and bath) is used for optimizing process parameters and feed particle distribution. As a second example, an advanced thermochemical model of a Ni-Cu sulphide smelting plant will be given. The on‐line model covers the operation of treating Ni-Cu-S concentrate via roasters, electric furnace and converters, producing a high grade Bessemer matte product for further refining. The model integrates the thermochemistry of the roasters and electric furnace, and predicts important process parameters such as degree of sulphur elimination in the fluid‐bed roasters, matte grade, iron metallization, slag losses and the iron to silica ratio in the electric furnace slag. Both models can be used to assist process engineers and operators in calculating the addition rates of coke, flux and air for different feed scenarios.

Jan 1, 2014

By Nagahiro Saito, Takahiro Ishizaki, Mituhito Hirota, Akio Fuwa

"Owing to their extremely high toxicity in the environment, the dioxins have been attracting social, technical and scientific attention in recent years. The authors theoretically had predicted the thermodynamic properties of all the dioxins via quantum chemistry and statistical thermodynamics and elucidated the generation-decomposition behavior of dioxins in the equilibrium calculation· of C-H-0-Cl system. In actual combustion processes, it is said that metallic compounds have much influences on the dioxins behavior. The aim of this study is to reveal the roles of metallic compounds the generation-decomposition behavior of dioxins is revealed from the viewpoints of quantum chemistry. Especially, the catalytic effect of copper has been investigated for the reaction, 2HCl(g)--H2(g}+Cl2(g) and for the etherification reaction from precursors, which is Phenol(g) here, to dioxins. The catalytic role of Cu is shown to have much influence on the generation -decomposition of dioxins.1. IntroductionIt is well known that dioxins are very harmful not only for our health but also for that of our children and grandchildren because they are very stable substance and their reaction rates of decomposition are considerably low. On the other hands, it is not well know how dioxins are generated and decomposed; the generation-decomposition conditions and paths as well as the catalysts to decompose them'1l. The authors believe that the thermodynamic and kinetic study of dioxins is useful to find a solution to these issuers. The authors have been investigating the following problems to reveal the generation-decomposition behavior of dioxins; (a) the prediction of the thermodynamic parameters of dioxins (2), (3), (b) the generation -decomposition behavior of non-chlorinated dioxins by the thermodynamic equilibrium calculations in C-H-O system(4) and (c) the generation-decomposition behavior of dioxins by the thermodynamic equilibrium calculations in C-H-O-CI system(5). Summaries of these thermodynamic researches are as follows.(I) The thermodynamic parameters for dioxins, which had been unknown and/or inaccurate'6 l, could be predicted and are available within the scientific accuracy."

Jan 1, 2000

By Huyang Xie, Rishi Raj, Vera A. Versteeg

"A new method for MOCVD has been developed in which a precursor solution is directly injected into a reaction chamber. The vaporization of short pulses of liquid is facilitated by atomization with a piezoelectrically-operated nozzle. The system has been used successfully to grow oriented, thin Ti02 (rutile) films on sapphire substrates with the crystalline relationship (101)[010]R I (1120)[0001]s. A growth rate of approximately 2 monolayers per pulse was achieved at 650°C for a reactant impingement rate of about 800 monolayers per pulse. Also, epitaxial LiTaO3 thin films were grown on (0001) sapphire from a single source, bimetallic precursor, lithium tantalum hexa-t-butoxide as the precursor. X-ray diffraction shows that the LiTaOa c-axis is normal to the sapphire surface. The x-ray pole figure and crosssection TEM diffraction show that the films were also in-plane oriented, with sapphire [1010] parallel to lithium tantalate [1010]. These films are shown to have extremely low optical attenuation, and refractive index that compares well with bulk values.IntroductionMetalorganic chemical vapor deposition (MOCVD) techniques have come into increasing use in recent years, due to the growing versatility and availability of precursors and improved environmental advantages over the halogenated compounds used for conventional CVD. Most commonly, the films are deposited by dissolving the metalorganic reactant (typically a metal alkoxide) in a carrier gas, which is carried through heated lines to a heated substratel . The metal alkoxides decompose by pyrolysis, leaving the films on substrates. While this method has been used to produce excellent epitaxial and heterepitaxial films, it has the disadvantages of complexity: the precursor must be heated to fix its vapor pressure, the gas flow rate carefully controlled, and the carrier lines heated to prevent condensation before reaching the reactor. Additionally, this conventional method cannot be used with certain low-volatility precursors that decompose upon heating."

Jan 1, 1994

By Lanre Oshinowo

Computational Fluid Dynamics (CFD) is used in conjunction with process modelling at HATCH to achieve a superior level of confidence in the process design of hydrometallurgical process plants. The use of these tools to evaluate designs through virtual prototyping reduces the risks associated with making design decisions. This paper highlights the development of a co-simulation strategy at Hatch for the seamless integration of process modeling software addressing different scales (process time and space): flowsheet level models and .equipment level models. With co-simulation, the process design engineers can improve design accuracy, troubleshoot and optimize performance and influence decisions impacting equipment operation by representing specific unit operations in the flowsheet model software with detailed CFD models. Specifically, this paper will focus on the co-simulation of a Ni/Co high-pressure acid leach (HPAL) process including heaters/heat exchangers and flash system, autoclave and quench/scrubber system. The knowledge developed can be transferable to other processes.

Jan 1, 2004

By Boxun Lu, Juan Wei, Kun Chen, Wanlin Wang, Lejun Zhou

"Slag system is an indispensable part during the continuous casting process, and playing various important roles like absorbing inclusions, modifying heat transfer rate, preventing oxidation of molten steel, etc. to ensure the smooth process and excellent slab quality. However most slags contains more than 8% fluorides which tend to introduce a series of environmental and health problems. This study involves the research of the removal of fluorine through the chemical composition optimization. Through the studies of CCT, DHTT, XRD and SEM, it has been successfully founded that the crystalline phase of Ca11Si4B2O22 discovered in this study shows very similar crystallization property as Cuspidine (Ca4Si2O7F2), which is the most important crystalline phase in the current fluorine bearing slags. Moreover, the optimized free/low fluorine slag shows the opportunity to replace conventional high-fluorine mold slag for casting medium carbon steels that is regarded as the bottleneck of green slag development for continuous casting.IntroductionMold flux has been widely used in continuous casting to control heat transfer, lubricate the strand, absorb inclusions, provide insulation and prevent oxidation of the molten steel[1-3]. It usually contains fluorides, like CaF2, NaF etc., which are used to control the viscosity and solidification temperature of mold fluxes [4-5]. However, the presence of fluoride leads to corrosion of equipment, serious environmental pollution (toxic volatiles and water pollution), and high processing cost of cooling water[6-7]. Therefore, the study of low or free fluorine mold flux is of interest and attracts worldwide attention.S. Y. Choi et al. [4] used B2O3 as a substitute for cuspidine in steel B2PB2) however, B2O3 content was extremely high (up to 30 w%). Other studies have investigated F-free mold flux by adding or optimizing components as MgO, Li2O, B2O3 et al[8-11]. However, most of these focused on the melting and viscosity issues or for low or ultra-low carbon steels, where crystallization tendency is not significantly strong. Very few studies regarding to the development of low/free Fluorine mold flux for casting medium carbon (MC) steels have been conducted, due to the difficulty of the crystallization and heat transfer control without the formation of cuspidine."

Jan 1, 2014

By F. E. Brinckman, G. J. Olson, D. Johnsonbaugh, T. K. Trout

"Microbiological metal recovery is an emerging technology likely to play an increasing role in commercial ore leaching, metal removal from process and waste streams, and perhaps ultimately in processing to yield metal products in specified forms or oxidation states. We are studying the potential for using microorganisms for the recovery of elements important to emerging materials technologies and for which domestic supplies are limited and/or low grade. Examples to be discussed include the bioaccumulation of yttrium and gallium. These elements are important in the production of new superconductor and semiconductor materials. However, limited domestic reserves and technologies for their recovery may cause supply problems. Microbiological processes may offer new techniques for recovery of these and other strategic elements.IntroductionMicroorganisms in ore leachingMicroorganisms assist in the commercial leaching of copper and uranium from low grade ores (1,2) and recently have been shown to have immediate commercial potential for the pretreatment of refractory gold ores to increase the gold-cyanide recovery yield (3). Copper bioleaching is the best known example of biotechnology applied to metal recovery. Copper can be recovered by commercial leaching of huge piles or dumps of low grade sulfidic ores and waste materials, which are not otherwise processable. Microbial activity in the leach dump environment oxidizes metal sulfides to soluble metal sulfates:"

Jan 1, 1988

By R. David Prenganan

RSR has developed a new environmentally superior process to recover lead as high purity electn:1o'i0!1 cathode from battery scrap. The process involves crushing the batteries, separating the lead bearing material from the plastic, ebonite and separators, and separating the active material (paste) from the metallic lead fraction. The paste is desulfurized using Na2C03 to convert the PbS04 to PbC03 and produce a sodium sulfate solution. The paste is further treated to decompose the PbO2 and PbC03 to Pbo. The PbO from the treated paste is easily leached, using H2SiF6 and electrown from solution using Pbo2?coated graphite anodes. The electrown lead has a purity exceeding 99.99%. RSR is in the final design stages of a plant to produce 36,000 tons per year of electrcwon cathode from battery paste in a new plant adjacent to the present Indianapolis refinery. This paper describes the work of a pilot facility operated in the early 1980's. The paper describes the patented process in detail and compares the newly designed environmentally clean electrolytic plant to present recycling plants.

Jan 1, 1990

By Yuanbo Zhang, Yingming Chen, Zijian Su, Bingbing Liu, Jun Chen

Iron, tin-bearing tailings is a kind of hazardous solid waste generated from cassiterite dressing operation. It is difficult to utilize the tailings by present mineral processing methods due to the complex dissemination characteristics. In this study, a process of gas-based magnetizing roasting followed by magnetic separation was studied for separating and recovering iron from the tailings. The effects of roasting and magnetic separation parameters on the recovery of iron were systematically investigated. The optimum parameters were proposed as follows: CO/(CO+CO2) content of 5%, roasting temperature of 850 C, roasting time of 60 min, grinding particle size of 90% less than 45 μm and magnetic field intensity of 800 Gs. Under these conditions, the magnetic concentrate containing 68.5% Fe and 0.06% Sn was achieved, which can be used as high-quality raw materials for direct reduction iron production.

Jan 1, 2016

By Shigehito Isobe

The Li-N-H system composed of LiH and LiNH2 catalyzed by titanium compound desorbs ~6 mass% hydrogen and a quite small amount of ammonia in temperature range from 150 to 250 °C under He flow atmosphere. In this work, hydrogen desorption (H-desorption) mechanism in the reaction from LiH+LiNH2 to Li2NH+H2 in a non-equilibrium condition was clarified by TDMS, TG and FT-IR analyses for the products replaced by LiD or LiND2 for LiH or LiNH2,respectively. The results suggested that H-desorption reaction progresses through two-step elementary reactions mediated by ammonia. As a next step, we carefully determined the amount of the ammonia containing in desorbed hydrogen for the Li-N-H system in a closed system from the practical point of view. The results indicated that a quite small of ammonia thermodynamically coexisted in the desorbed hydrogen in closed system, although ammonia could not be almost detected in emitted hydrogen gas by TDMS under some non-equilibrium conditions. Moreover, for understanding the role of titanium, the chemical bonding state of the titanium compounds doped as catalyst in the mixture was examined by XAFS measurement. The results indicate that the Ti atoms, which can induce catalytic effect, are in a particular chemical bonding state.

Jan 1, 2006

By Kafui Nyavor

The indirect, and the direct contact mechanisms of bacteria oxidation of sulfides were studied using Thiobacillus ferrooxidans and pyrite. The aim was to determine which of the two generally aeeepted mechanisms played a dominant role, if any, during acid mine drainage (AMD) formation from the oxidation of sulfide minerals. The results show that at a pH of 4.5 where T. ferrooxidans are quite active, but where initial chemical oxidation of pyrite to Fe2+ is limited, the bacteria were unable to directly oxidize pyrite to any significant extent. Whereas, in the presence of Fe2+, T. ferrooxidallS assisted oxidation of pyrite by the indirect mechanism was observed and sustained over the pH and Eb range where the bacteria is active. The results lead to the conclusion that the direct contactmechanism of pyrite oxidition by T. ferrooxidans is insignificant. The predominant, and possibly the only, pathway involves the indirect bacteria oxidation of available Fe2+ to Fe3+, which in turn oxidizes FeS2 to generate additional Fe2+ and acidity in a cyclic process.

Jan 1, 1996

By M. Save, N. Menad

"This paper gives the overview of different alternatives to recycle the following wastes: slag, dusts, wastes of electric and electronic equipment (WEEE) and auto shredder residues (ASR). Based on modified Bogue calculations, steelmaking slags were combined in order to produce a belite-rich clinker activated with sulphoaluminate. The EAF dusts containing significant amount of metals can be recycled in different ways: The carbothermal treatment and INTECT process are reported. The results obtained from the model of Auto Shredder Residue injection into blast furnace show that ASR can be used as reducing agent in the BF process if certain conditions are met. The particle size of this material must be controlled to ensure optimal gasification of the material in raceway. The non-ferrous contents may affect the pig iron quality, which is difficult to rectify at a later point. It seems the pyrolysis is the most attractive process to handle ASR. The BRGM flow sheet of WEEE treatment is also reported.I. Introduction The activities of human been may generate wastes and by their accumulation during several years, these wastes may have an impact on the environment and on the human health. These wastes can be generated in the forms of solid, liquid and gas. A variety of industrial wastes can be recycled for use as products. There are three ways in which industrial waste recycling occurs: at the facility itself (on-site recycling), at commercial facilities that gather waste streams from several companies (off-site recycling), and at a company that uses as inputs in its production process the waste products of another company. The industries producing iron and steel may generate different solid wastes which are classified in three main categories: 1. Ferrous material (mainly dusts and sludges from gas cleaning), 2. Slags (these by-products are generated from different process stages), 3. Others by-products (including refractories and material generated from engineering activities). According to this review, the most quantity of the metallurgical wastes is deposed. Currently, the public opinion opposes the creation of new sites. This leads to the growth of the waste disposal costs. Such situation reduces the enterprise competitiveness and decreases their market share on regional and/or national and/or world scales. In these conditions, the economical activities can be decreased leading probably to social problems. The problem of wastes and/or by-products can be treated on three levels:"

Jan 1, 2008

By Kathryn A. Mrotek

The textural growth patterns of nodules from two areas in the North Pacific and the South Pacific are characterized by mottled, columnar and compact-type zones. Amorphous material (mainly iron and manganese hydrox-ides) is a botryoidal-forming phase in the mottled and columnar zones. Crystalline material (platy crystals of birnessite and crystallites of todo-rokite) is found primarily in the mottled zones on botryoidal structures or as long-protruding structures growing onto that portion of the nodule in contact with the underlying sediments. The long-protruding mottled zones contain little or no biogenic debris, suggesting that these zones grew un-interruptedly within the underlying sediments. The coalition of spheroidal knobs comprising some of the nodules also suggests a relatively long residing time within the sediments. It appears that crystalline material (the usual host to associated valuable metals) forms in a quiet environment and as a result of direct nodule association with the underlying sediments.

Jan 1, 1982

By David Cocke

Study of surface and subsurface interfacial chemistry of metallic and similar systems has its enormous technological importance. Copper, for example, is a common component of many alloys and bulk amorphous systems. It is being increasingly studied today because of its use for electronic interconnect systems where processing is done below 200 ºC. Since several types of copper oxides exist, and the degree of their formation is dependent on temperature, perhaps characterization by EDS-SEM depth profiling and EIS might delineate one type of oxide from another. In this paper, we described our work on transformation of copper oxides with temperature ranging from 70 to 350 °C and their characterization by SEM, EDS, and XRD. We also showed the use of the phase angle portion of the impedance as a means to identify the predominant structure and the transition through Cu3O2 between the predominant stable CuO and Cu2O.

Jan 1, 2009

By A. S. Block-Bolten

Two innovations in nickel-arsenic separation have been studied on a laboratory scale. The first requires only a nitric acid atmospheric leach without preliminary roasting and leads to favorable final conditions for precipitation of arsenic as highly stable FeAsO4, The second is an NaOH-H2O2 pressure leach which is an alternative to the known NaOH-O2 pressure leach. Either method offers the possibility of rapid and efficient separation of nickel from arsenic and is applicable, for example to the high grade niccolite deposits in the Great Slave Lake area of northern Canada.

Jan 1, 1982

By A. Cullaj

Several industrial sites suffer from the contamination of soils from heavy metals, which are emitted among others by anthropogenic mining and metallurgical activities. Effective and economic physicochemical technologies for remediation of these sites remain complicated and costly. A new alternative remediation technique is the so-called phytoremediation. This is based on the ability of some plants to accumulate very high concentrations of metals from soils and thus providing the basis for a remediation of the contaminated sites. This technique as an emerging branch of natural biotechnology, has several advantages compared to the sophisticated physicochemical techniques of soil remediation. It is not only environmentally friendly but also its costs are quite low since it is solar driven. Furthermore plants can accumulate metals to such levels that the mineral recovery maybe feasible even in conventional Ni refinery or smelting operations. In this work, thc potential of many plants to accumulate nickel has been investigated in order to identify the species which offer the best phytoremedial potential for nickel contaminated soils in Albania. Field surveys have been made in five nickel-containing sites in order to identify the nickel tolerant species that have spontaneously grown in contaminated soils. Atomic Absorption Spectrometry measurements were carried out on 145 different plants collected. 16 of them were identified as having an hyper ability to accumulate nickel since they contained more than 10 000 mg Ni per kg (DW). Seven taxa are of Alyssum genus and one of Bornmuellera genus of Cruciferae. The highest accumulation of nickel was present in aerial parts of Alyssum murale var. chlorocarpum Hausskn (25 500 mglkg or 2.5%) and Alyssum markgrafli O.E. Schulz (23 700 mg/kg or 2.37%). The seeds germinated are more evidenced at A.m.var. chlorocarpum, about 63%. These plants are suggested as the most promising species to be used for phytoremediation purposes in nickel contaminated soils and phytoextraction of nickel.

Jan 1, 2003

By A. Cullaj

Several industrial sites suffer from the contamination of soils from heavy metals, which are emitted among others by anthropogenic mining and metallurgical activities. Effective and economic physicochemical technologies for remediation of these sites remain complicated and costly. A new alternative remediation technique is the so-called phytoremediation. This is based on the ability of some plants to accumulate very high concentrations of metals from soils and thus providing the basis for a remediation of the contaminated sites. This technique as an emerging branch of natural biotechnology, has several advantages compared to the sophisticated physicochemical techniques of soil remediation. It is not only environmentally friendly but also its costs are quite low since it is solar driven. Furthermore plants can accumulate metals to such levels that the mineral recovery maybe feasible even in conventional Ni refinery or smelting operations. n this work, the potential of many plants to accumulate nickel has been investigated in order to identify the species which offer the best phytoremedial potential for nickel contaminated soils in Albania. Field surveys have been made in five nickel-containing sites in order to identify the nickel tolerant species that have spontaneously grown in contaminated soils. Atomic Absorption Spectrometry measurements were carried out on 145 different plants collected. 16 of them were identified as having an hyper ability to accumulate nickel since they contained more than 10 000 mg Ni per kg (OW). Seven taxa are of Alyssum genus and one of BornmueIIera genus of Cruciferae. The highest accumulation of nickel was present in aerial parts of Alyssum murale var. chlorocarpum Hausskn (25 500 mg/kg or 2.5%) and Alyssum markgrafii O.E. Schulz (23 700 mg/kg or 2.37%). The seeds germinated are more evidenced at A.m.var. chlorocarpum, about 63%. These plants are suggested as the most promising species to be used for phytoremediation purposes in nickel contaminated soils and phytoextraction of nickel.

Jan 1, 2003

By Tong Zhilin

The reasons why the pits were formed on the cathode in the process of Ni electrowinning and the methods how to prevent these pits from forming are described. Some examples are presented. It has 'been proven that P507 and P204 present in the electrolyte can effectively prevent pits from forming on the cathode.

Jan 1, 1993

By Deventer Johanna van

Ore bodies around the world are declining in grade, whilst increasing in complexity. The level of impurities relative to the valuable metal is steadily increasing, posing new challenges to existing operations. Ion exchange is widely used in the hydrometallurgical industry for both primary recovery of metals and the removal of impurities. The superior selectivity of ion exchange resins makes them exceptionally suitable for the removal of target impurities to very low levels, thereby saving operating costs, increasing the value of the final product and significantly improving revenue. The ion exchange process in these applications is very simple, using standard ion exchange equipment and acid regeneration. The process can be fully automated, requiring minimal operator interference and supervision Examples of impurities that are successfully removed via ion exchange include iron, antimony and bismuth from copper electrolyte. In the copper electrolysis process, antimony, bismuth and arsenic tend to form slimes which are dispersed in the electrolyte. These slimes contaminate the cathode and/or decrease the quality of the copper deposition. A special chelating resin was developed to remove antimony and bismuth, while at the same time ensuring minimal chloride leakage to the sulphate matrix. The work is described in more detail in this paper. Ion exchange is also used to remove copper, zinc and nickel from cobalt electrolyte. This paper addresses a few of these examples in more detail.

By D. H. H. Quon

Results of a study conducted to determine the properties of iron ore pellets made from Mount Wright and Carol Lake ore concentrate fines with partial and full substitution of bentonite by several organic binders are presented. Carboxy methyl celluloses 7H and 6TL, hydroxy ethyl cellulose (natrosol) and modified guar gum all produce pellets of acceptable wet, green and dry strength. However, when fully substituted, an inorganic binder such as calcium carbonate is required for satisfactory strength development after induration. Mixing the Carol Lake ore with Mount Wright ore in a 50-50 ratio also achieves the same result. The failure of the Carol Lake ore in the pelletization process is attributed to the low hematite content of the ore. The results are very similar to those from the extrusion studies reported earlier (8).

Jan 1, 1989