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By T. Wang, R. G. Reddy, D. Mantha

"A new eutectic LiN03-NaN03-KN03-KN02 quaternary molten salt system was calculated using thermodynamic modeling. The eutectic temperature was predicted to be 100°C. The melting point and heat capacity of the salt eutectic composition were determined using DSC. The experimentally determined melting point is in excellent agreement with the predicted value. The melting point is more than 124°C lower than that of the KN03-NaN03 solar salt. The density of the molten salt was experimentally determined as function of temperature. Using the density, heat capacity and the melting point, thermal energy storage density and gravimetric storage density of the quaternary molten salt were calculated and compared with that of solar salt. The larger storage density value of this molten salt indicates that this salt has a better energy storage capacity for solar power generation systems.IntroductionMolten salts have been used as thermal energy storage media for solar energy applications. Nitrates are being used in the solar energy applications for their low melting point, low unit cost, high heat capacity, high thermal stability, negligible vapor pressure and high energy storage density [l]. Solar salt (NaN03/KN03: 60/40) is the most popular thermal energy storage medium which is currently being used with the freezing point of 221 ·c [2]; another ternary system HITEC® which contains NaN03, KN03 and NaN02 has freezing point of 141°C [3]. Newer nitrate salt mixtures are being studied and projected as potential candidates for thermal energy storage (TES) and heat transfer (HT) applications. Based on these favorable features, molten salt can work directly as the energy storage medium below 500°C [l]. Development and synthesis of newer molten salt mixtures with freezing point lower than those currently used for thermal energy storage applications is necessary for sustained utilization of solar energy. The approach to develop lower freezing point molten salt mixtures is by the prediction of new eutectic mixtures and also by the development of new nitrate compounds."

Jan 1, 2012

By R. A. Roberti

Most copper refineries use conventional wheel systems to cast anodes. over a period of time the copper moulds that are used become warped and cracks develop. To control mould warpage, the mould's are either rejected after a certain warpage is reached, or the shape is restored by mechanical means. The cracks, unless they are very severe, are repaired by a peening process. Even with regular maintenance to control warpage and cracks, the moulds have a limited useful life. If warpage and cracks are not controlled, anode quality deteriorates and tankhouse operations are seriously affected. -An intensive study was initiated to develop means of controlling mould warpage which culminated in the d?evelopment of technology to control mould warpage to within ±1. 5 mm, and at the same time effectively contr0l: cracking and significantly increase the mould life-. The warpage control has been achieved by using a unique mould design. Mould cavities are present on both sides of the mould and periodic inverting controls the wa-rpage in the cavities. The mould casting procedure has been developed and all production wheels have been converted to the new mould design. The performance characteristics of these moulds will be detailed. 21

Jan 1, 1987

By Takaaki Shibata

The Tamano Refinery has developed two new processes for removing the impurities, arsenic, antimony, and bismuth from an electrolyte. The first process involves bleeding the surface electrolyte in the electro-refining cells. The copper concentration level in the outermost layer is lower than that in any of the other layers, while the impurity levels are almost the same in all layers. Bleeding the surface electrolyte increases the amount of impurities removed in the liberator by approximately 20%. The second process involves adsorbing antimony and bismuth from the electrolyte by means of chelating resin. As the electrolyte passes through the packed column of chelating resin, antimony and bismuth are selectively adsorbed. They are then desorbed by means of hydrochloric acid, and then recovered in the form of a highly concentrated antimony chloride solution by means of evaporation. This process almost doubles the capacity for removing antimony from an electrolyte.

Jan 1, 1987

By J. D. McCain

Magma's San Manuel smelter has adopted new operating techniques resulting in 21% increased productivity and 87% reduction in lost time accidents. Reverberatory furnaces were converted to coal firing from expensive natural gas and fuel oil. Slag and matte flow problems and safety were improved by implementing hydraulic slag stopping and matte tapping machines. Coordination of furnaces, converters and acid plant was improved by using a computer-aided converter controller/scheduler function. Manual mudding of converter lips after each collar pull was replaced with a gunning system for coating the mouth castings. One converter punch car was automated using robotic technology. An automatic anode take-off was installed with fewer moving parts and a mechanism for ear twisting one cell contact. Anode copper refining was improved by replacing propane/hydrogen mixtures with high pressure/velocity natural gas tuyeres. Improved converter scheduling increased acid plant production 43% with more autothermal operation time. Six dedicated computers/microprocessors are utilized for automation, data acquisition, process monitoring and on-line air quality information for the Supplementary Control System.

Jan 1, 1983

By D. Lui, B. G. Thomas, B. Ho

"Results from mathematical models and plant experiments are combined to quantify the effect of transverse depressions and oscillation marks on heat transfer in the continuous casting mold. A heat transfer model has been developed to calculate transient heat conduction within the solidifying steel, coupled with the steady-state heat conduction with the continuous casting mold wall. The model features a detailed treatment of the interfacial gap between the shell and mold, including mass and momentum balances on the solid and liquid powder layers. The model predicts the solidified shell thickness down the mold, temperature in the mold and shell, thickness of the resolidified and liquid powder layers, heat flux distribution down the mold, mold water temperature rise, ideal taper of the mold walls, and other related phenomena. The important effect of non-uniform distribution of superheat is incorporated using the results from previous 3-D turbulent fluid flow calculations within the liquid cavity. Results from plant experiments confirm that transverse surface depressions and oscillation marks form at the meniscus and move down the mold. Measurements of mold thermocouple temperatures and breakout shell thickness were used to calibrate the models. The results indicate that the surface depressions and oscillation marks are filled with mold flux, but still have a significant effect on decreasing heat transfer. The predicted mold temperature fluctuations are consistent with measurements. If the depressions become filled with air, their effect is greatly increased. These results should be useful in the difficult task of interpreting transient mold thermocouple signals for on-line quality monitoring.IntroductionMany different types of intermittent surface defects on steel slabs arise during initial solidification in the mold of the. continuous casting machine. These defects include deep oscillation marks, surface depressions, and cracks. They may lead to quality problems, such as slivers, in the final rolled product. In severe cases, breakouts may occur, where liquid steel bursts through a thin section of the shell and drains over the casting machine below the mold."

Jan 1, 1997

By W. J. Mitchell

During the months of April and May 1992, the Phelps Dodge Hidalgo smelter underwent a major turnaround. This was the third such turnaround in the life of the facility which was commissioned in 1976. During the third furnace campaign, the smelter processed 5.2 million tons of concentrate producing 2.6 billion pounds of anode copper over a 7.5 year period. The critical path on the fifty-nine (59) day turnaround schedule was the reconstruction of the Outokumpo flash furnace which integrated some modifications with standard rebuild practices. Modifications included incorporation of horizontal cooling jackets throughout the furnace settler as well as the installation of castable refractory in the reaction and uptake shafts.

Jan 1, 1993

By G. Gao

Flyash from municipal solid waste (MSW) incinerators is frequently classified as a characteristic hazardous waste due to its lead and cadmium content. Extensive investigation has therefore been carried out to detoxity the flyash by leaching and to recover lead, cadmium and zinc. Detoxification can be accomplished by leaching in HCI/NaCI solutions. Optimization of leaching conditions for effective detoxification and subsequent metal recovery can be achieved by controlling the acidity of the lixiviant and flyash to lixivaint ratio. Lead and cadmium In the leaching solution is recovered by cementation with zinc dust. Leaching and cementation experiments have shown that zinc concentrations suitable for electrowinning, > 15 g/liter, can be achieved. Experiments have also been performed to determine the effects of pH, particle size of the zinc dust used, quantity of zinc added and dissolved impurities on the cementation kinetics. After recovery of lead and cadmium, electrowinning or electrowinning coupled with solvent extraction can be used to recover zinc. A process flowsheet is presented.

Jan 1, 1991

By D. G. Hattingh, A Els-Botes

"Considerable information is available on the factors influencing the iron-zinc reaction rate at 450° C of low carbon steels, in comparison there is a scarcity _of similar fundamental information of spheroidal graphite irons. This can be attributed to the more complex microstructure and ferrous alloy chemical analysis of spheroidal graphite irons. Hot-dip galvanizers have identified the complexity in controlling and predicting the thickness of the galvanized coating formed on commercial cast irons, which has serious financial implications for both the galvanizer and customer.Commercial hot-dip galvanizing has been in use for over 160 years and yet an elementary understanding of the dynamics associated with the hot-dip galvanizing of spheroidal graphite cast iron is still insufficient. To allow the. process to become a modem surface engineering technology, the fundamental aspects of the process must be thoroughly understood.When a clean iron or steel article is dipped into the molten zinc, zinc initially solidifies around the steel or iron. As heat is transferred to the article form the bath, this initial solidified zinc layer remelts and a series of iron-zinc alloy is formed by the reaction of the zinc with the surface of the article; on removal from the bath, some of the molten zinc is taken out on top of the alloy layers. At normal galvanizing temperature (450 °C), the reaction between iron and zinc is usually parabolic with time. The rate of reaction is rapid at first but then slows down and the coating thickness does not increase greatly if the article is immersed in the bath for longer times(1)."

Jan 1, 2000

By S. M. Hay

The zinc content of blast furnace and basic oxygen furnace dusts is low compared with electric arc furnace dusts and it is generally not economical to treat the dusts to recover zinc. However, they have a high iron content and removal of the zinc would allow recovery of the iron values. A literature review and thermodynamic analysis was undertaken and, as a result, several smelting options were identified. This paper describes experiments undertaken to develop understanding of metallurgical aspects of these processes which are not amenable to theoretical analysis. Dusts from an Australian steelworks were characterised in order to determine their mineralogical make-up and the form of the iron. The processing aspects investigated in the laboratory were slag-metal equilibrium and solid-state pre-reduction using reducing gases of compositions expected from bath-smelting processes. Particular attention. was paid to the deportment of zinc, sodium, potassium, phosphorous and sulfur between the phases formed during smelting and pre-reduction. The smelting results indicate that less than 10% of the zinc, sulphur, sodium and potassium report to the metal. About 99% of the zinc and potassium and about 80% of the sodium could be volatilised from the dusts by reducing them at 1,000°C with mixtures of CO, CO2, H2 and H2O even when metallic iron was not formed. The experiments indicate that smelting of blast furnace and basic oxygen furnace dusts should produce hot-metal of a composition which can be blended into the main stream of hot-metal in the steelworks.

Jan 1, 1994

By W. K. Collins

Engineered Scavenger Compounds (ESCs), developed by the U.S. Bureau of Mines, are a novel class of compounds that can selectively recover a desired element from a solid or molten alloy. Lithium titanate (Li2Ti3O7 or L'20-3T'02) is being used as an ESC to recover lithium (Li) from Aluminum-Lithium (Al-Li) alloys. X-ray diffraction measurements have shown that lithium titanate undergoes a phase change from an orthorhombic structure to a hexagonal structure. This change is due to the incorporation of Li in the matrix of the material and the effect of temperature. Although both are metastable, the hexagonal phase that forms during the scavenging of Li from Al-Li alloys appears to be the more stable phase. Recovering Li from the ESC by electrodeposition does not cause the structure to revert to the orthorhombic phase. Both the orthorhombic and the hexagonal structures of Li2Ti3O7 have similar scavenging capacities for Li. This paper proposes a new mechanism for the phase transformation.

Jan 1, 1993

By Jing Zhan

The fibrous precursor can be obtained by coordination precipitation process, using oxalate, cobalt chloride and ammonia. The composition and morphology of fibrous precursor were characterized by XRD, IR, DTA/TGA and SEM analysis. The results show that XRD pattern and composition of the precursor with fibrous morphology precipitated at pH=9.0 were different from that of ß-CoC2O4?2H2O precipitated at pH=1.0. The mechanism on the thermal decomposition of fibrous precursor was addressed. The influences of various conditions in pyrolysis, including the temperature, time, atmosphere, and the morphology of the precursor, on the morphology, average size and specific surface area of the Co powders were investigated in detailed. At last, the final product, fibrous cobalt powders with diameter about 0.3~0.5µm in size and 40~60 in aspect ratio, were produced by thermal decomposition at 400~500? in the weak reducing atmosphere. The structure of pores in cobalt powders was capillary tube with open ports and the majority was mesoporous.

Jan 1, 2009

By Ryosuke O. Suzuki

A new cell concept for calciothermic reduction is proposed in which the titanium dioxide instead of TiCl4 is used as the raw material for reduction, Metallic calcium is needed as the reductant of a thermochemicaily stable oxide, such as TiO2. CaCl2, is selected as the solvent of Ca and simultaneously as the solvent of CaO. The reduction system consists of a single cell where both the reduction reaction and the electrolytic reaction for recovery of reducing agent coexist in the same molten CaCl2 bath. A few mol%Ca dissolves in the melt and gives the media a strong reducing power. Sufficiently deoxidized metallic titanium deposits and forms a slightly sintered granular sponge. Both mechanisms of the halide flux deoxidation and the electrochemical deoxidation work efficiently for these fine precipitates, The reducing agent is in situ recovered by electrolysis of CaO because the molten CaCl2 he a relatively large solubility for CaO Some cell designs and modifications are proposed for industrial applications.

Jan 1, 2003

By D. Donald Downey

Pilot Testing Ion Exchange Resin (IEX) can go from very simple beaker testing to complicated column testing. Space velocities, regenerant quantities, loading capacities, ion leakage, are all terms that get accumulated together to prove or disprove a resin’s (or resins’) ability to load a single ion (or specific set of ions). Not getting all the resin’s operating parameters correct will disqualify (or at least skew) the results. Laboratory tests for capacity, moisture content, bead size, metals fouling, etc.—what does it all mean? At last count, there were over twenty-five separate ion exchange resin tests (analyses) that were available to end users. Standard testing procedures identify the resin properties but more specific procedures can be used to identify problems with equipment operation. Then, there are the costs to consider; simple cation resin testing (moisture content, total capacity and bead integrity) is in the $200/sample range. However, add to this Chatillon, Russian Ball Mill Test, HIAC particle size, metals and % regeneration test procedures and the lab work can increase to over $1000/sample. In this paper, the author will explain the “must-do” pilot and test procedures and why they are important and the key to understanding how resin performs ion exchange.

By D. Raghavan

In recent years, the environmental issues related to the landfill shortage received considerable importance. Many polymeric solid wastes have high resistivity to chemical and biological degradation, and options are sought by which these wastes can be recycled and reused, or reduced in volume. The present study investigated the biodegradation of polyethylene by Aspergillus niger, and biodesulfurization of rubber by pure and mixed cultures of Thiobacillus thiooxidans and Thiobacillus ferrooxidans. The fungus, A. niger, was found to metabolize portions of polyethylene. Quantitative calorimetric measurements revealed that the amorphocity of the sample decreased during biodegradation. Removal of sulfur from synthetic rubber samples containing 2 to 15% sulfur, was studied in shake flask experiments and the associated oxygen consumption was studied in Warburg respirometers. The mixed bacterial cultures were more effective in the desulfurization of rubber samples than the pure cultures of T. thiooxidans and T. ferrooxidans. The data obtained in these studies may have far reaching consequence for the development of new effective processes regarding the remediation and management of discarded polymeric packaging wastes and car tire rubber materials.

Jan 1, 1993

By Carlos Mauricio Fontes Vieira, Sergio Neves Monteiro, Thiago Samarão Motta

This work has as its objective to characterize ceramic bodies formulated with ornamental rock waste and two different clays to produce ceramic paver. Specimens were made by uniaxial press-molding at 20 MPa and then fired at 950 and 1050oC respectively. The determined technological properties were: plasticity, dry bulk density, linear shrinkage, water absorption and flexural rupture strength. The results showed that the type of the clay has strong influence on the properties of interest for heavy clay ceramics. The investigated waste must be incorporated in small amounts to avoid increasing in the porosity of the ceramics.

Jan 1, 2015

By G. H. Khoe

Neutralisation of acid uranium mill tailings with lime or other alkaline materials is usually practised to reduce the dissolved concentration of heavy metals and radio nuclides. Computer modelling of this process was carried out using the geochemical equilibrium code MINTEQA2. Computed dissolved metal and sulfate concentrations were compared with laboratory-based experimental data. It was found necessary to include the modelling of adsorption of trace metals (such as uranium and lead) by the precipitated ferric hydroxide in order to obtain acceptable concentrations in the neutralised liquors. There were limitations of the modelling exercise due to important aspects which were not addressed or properly accounted for such as chemical reaction kinetics and the effect of high ionic strength. These are discussed in the paper.

Jan 1, 1991

By L. A. Bertram, F. J. Zanner

"The goal of this paper is to present a tool to simulate transient melting of the electrode tip. This capability is needed to develop and test furnace control algorithms since experimental determination is difficult and expensive. Simulation incorporates parameters (including arc voltage, arc current, electrode gap and furnace pressure) from previous quasi steady experiments with 460 mm diameter Inconel 718 electrodes.Cathode heating rates (determined by classical as well as experimental arc models) are linked to these independent variables. After radiative loss adjustments to the heating, transient one dimensional melting is computed. IntroductionThe vacuum arc remelting (VAR) process attempts to improve the physical and chemical homogeneity of a static-cast electrode by remelting and solidification in a quasisteady manner. To achieve steadiness of furnace operation requires automatic controls based on inputs measuring physically relevant state variables of the process. Previous industrial scale VAR studies (1,2,3) involving stainless steels, superalloys, and other alloys have provided a basis on which control strategies of some generality can be proposed (4). Of these measurements, the data for Inconel 718 is the most complete, so discussion in this paper is restricted to this alloy.Studies of the In 718 alloy subjected to the VAR process have established that melt rate M (kg/hr) depends not only on the melt current 1m (kA) supplied to the furnace, but also on ambient gas pressure of CO, PCO (micron), and electrode gap ge (mm) as well (1):"

Jan 1, 1986

By Wenxian Zhu, Xuema Li, Patrick R. Taylor

"Experiments were performed in a non-transferred arc, thermal plasma flow reactor to investigate the synthesis of ultra fine boron nitride (BN) powder from the reaction system of boron oxide (Bz03), methane (CH4), ammonia (NH3) and hydrogen (H2). Argon (Ar) and nitrogen (N2) were used as plasma gases. The thermodynamics and kinetics of the synthesis reactions were examined and a chemical reaction mechanism was proposed. The powders produced under certain operating conditions had high purity and good conversions. All the products were extremely fine powders (< 30nm) and were uniform in size distribution. The powder products were analyzed by chemical and physical characterization. The effects of the reaction variables on the conversions from B203 to BN and the purity of the products were investigated.IntroductionIn the past few decades, boron nitride (BN) has attracted a great deal of interest because of its excellent thermal, chemical and electrical properties (1-4) It has a high thermal stability and thermal conductivity. Chemically, it is very stable and is not wetted by most molten metals and slag. It is also an excellent low loss insulator. Since hexagonal boron nitride (h-BN) is light in weight, strong and easily fabricated, it has applications in a variety of specialized high temperature areas, such as a high temperature lubricant, crucibles for molten metals, thermocouple protection tubes, break rings for horizontal continuous casting of steel, and friction reducing coatings. In cubic form, boron nitride is one of the hardest materials known, second only to diamond, and it is an excellent material for tools in which the use of carbon based materials is limited by oxidation or reaction with metals."

Jan 1, 1998

By C. Acuna

The standard procedure of fire refining consists of sulphur removal via air injected through tuyeres, arsenic slagging via soda-lime flux and oxygen reduction by air or oxygen deficient air or a steam fuel mixtures. The use of porous plugs to stir with an inert gas has been mainly considered as a surface renewing agent that increases the product quality and shorten the refining cycle. In the present study the effect of the bottom stirring by nitrogen gas injection through porous plugs for the treatment of the crude copper in the range of 400-150 ppm sulphur, 3,000?2,000 ppm arsenic and 14,000-7,000 ppm oxygen content was investigated. The combined effect stirring-reducing, by the use of air or a steam fuel mixtures through tuyeres for oxygen removal, follows a kinetics of first order where the constant, K, can be represented by the following polynomial expression: K = A .* R2 + B * R + C Where A, Band C are constants that depend on the nitrogen flow rate and R is the air-fuel ratio or the steam-fuel used in the reducing step. Depending on the optimization of the flow of nitrogen and the air-fuel or steam-fuel mixture and only if just the oxidation, complexing and reducing steps are considered, the process cycle might be shortened by 45%.

Jan 1, 2003

By Jun Enriquez

Kennecott Utah Copper aims to extend anode furnace campaigns to more than three years. As part of that goal improvements are sought on anode-furnace tuyere-area refractory performance. Kennecott and Praxair developed high pressure nitrogen refining for the Oxidation Stage which shortened anode furnace fire refining cycles by up to two hours per cycle. Future developments include optimizing the Reduction Stage’s steam-gas reforming and achieving coherent jet tuyereless refining.