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By James A. Voigt

"The efficient separation of metal species from aqueous streams by precipitation techniques requires a fundamental understanding of the various processes that occur during precipitation. These processes include particle nucleation, particle growth by solute deposition, agglomerate formation, and agglomerate break-up. The application of the population balance approach has been used to develop a kinetic model that accounts for these competing kinetic processes. The usefulness of the model is illustrated through its application to the precipitation of yttrium hydroxynitrate, YHN. The kinetic parameters calculated from the model equations and system specific solution chemistry are used to describe several aspects of the effect of pH on the precipitation of the YHN. Implications with respect to the simultaneous precipitation of more than one cation type are also discussed through use of example systems. The effects of solution chemistry, precipitator design, and solvent choice are considered.IntroductionThe application of precipitation technologies to the separation of metals from solution is widely used. Regardless of its application, be it in such diverse areas as the preparation of metal oxide powders for use in commercial products or as a unit operation in the removal of trace metals during wastewater clean up, the fundamental processes involved are the same. These processes include: nucleation from solution, either homogeneous or heterogeneous; growth from solution with chemical reaction either in solution or at the precipitate/solution interface; growth by particle agglomeration; and particle break-up by collisional or shear forces. The effectiveness of the operation and the properties of the precipitate formed, or ""quality"" of the product, are determined by the competing kinetics of the different processes. The kinetics of the processes, in tum, are determined by system-specific solution chemistries and the conditions used to carry out the precipitation operation. For example, generally, when system conditions are such that the supersaturation driving force for precipitation is very high, growth species normally do not have the time to organize themselves with a high degree of crystallographic order and the precipitate is amorphous. In this case nucleation rates are invariably extremely high and the primary mechanism for growth is the agglomeration of nuclei. Conversely, when the supersaturation levels for the same system are reduced, the kinetics of the nucleation and growth processes also are greatly reduced, and a crystalline precipitate can be formed, since the growth species have time to order on particle surfaces."

Jan 1, 1996

By Ruiling DU, Jiazhi Zhang, Yong Zhao, Keng Wu

Reaction kinetics of metallurgical physical chemistry which was successfully applied in metallurgy (as ferrous metallurgy, non-ferrous metallurgy) became an important theoretical foundation for subject system of traditional metallurgy. Not only the research methods were very perfect, but also the independent structures and systems of it had been formed. One of the important tasks of metallurgical reaction engineering was the simulation of metallurgical process. And then, the mechanism of reaction process and the conversion time points of different control links should be obtained accurately. Therefore, the research methods and results of reaction kinetics in metallurgical physical chemistry were not very suitable for metallurgical reaction engineering. In order to provide the definite conditions of transmission, reaction kinetics parameters and the conversion time points of different control links for solving the transmission and reaction equations in metallurgical reaction engineering, a new method for researching kinetics mechanisms in metallurgical reaction engineering was proposed ,which was named stepwise attempt method. Then the comparison of results between the two methods and the further development of stepwise attempt method were discussed in this paper. As a new research method for reaction kinetics in metallurgical reaction engineering, stepwise attempt method could not only satisfy the development of metallurgical reaction engineering, but also provide necessary guarantees for establishing its independent subject system.

Jan 1, 2015

By K. G. Wang, M. E. Glicksman, P. Crawford

"We formulate the mathematical solution to late-stage multi particle diffusion in finite systems. The transition from finite system behavior to that for an infinite system is established. Large-scale simulations are reported regarding the dynamics of phase coarsening. Even in the case of a small volume fraction (Vv = 10-4), the particle size distribution is broader than that for the well-known Lifshitz-Slyozov limit at zero volume fraction. We also report the first simulation studies of extremely low volume fraction, for which corresponding experiments, as well as other simulations, do not exist at present for comparison. However, in the case of moderate volume fractions (Vv = 0.1), the fiucutations in the volumetric growth rate of particles are extracted from our simulations. These simulations provide additional insight into the statistical nature of diffusion interactions, including multiparticle stochastics during microstructural evolution.IntroductionPredicting microstructure evolution in alloys remains one of the cornerstones of materials science. Phase coarsening is a common process in microstrucural evolution that leads to a decrease in the excess total interfacial energy of the system. The system typically consists of separate and identifiable units, or domains, such as second-phase particles distributed in a matrix. During phase coarsening, larger particles grow at the expense of small particles. Over time, this ""competition"" results in an increase in the average size of the particle population, and in a concomitant decrease in the number of particles.Particle size and microstructure of many cast alloys depend on similar coarsening processes. Indeed, properties of these materials, such as strength, toughness, ductility, and electrical conductivity, depend on the material's average particle size and particle size distribution (PSD). Understanding and controlling microstructures in two-phase systems are clearly of widespread technological importance."

Jan 1, 2001

By Eric J. Beckman

Recovery of metals from dilute solution, whether the matrix is solid, or liquid, remains a considerable technical and financial challenge. Methods currently exist whereby metals can be extracted from either type of matrix, yet these methods consume significant quantities of reagents and can also generate multiple waste ,streams in the process. Technology developed in our lab allows efficient application of environmentally-benign CO2 to a number of separation problems involving metals. For example, we have employed biphasic mixtures of C02 and water as a green acid leach medium. Metals have been extracted from a steelmaking process residue and then recovered as metal carbonates through depressurization. In this process, metals are extracted and recovered without the use of reagents other than CO2 and water, and CO2 is sequestered as a solid. In addition, through synthesis of Cal-miscible phase transfer agents, we have shown that CO2 can replace the organic solvent currently used in refining of precious metals, The sensitivity to pressure of phase behavior in a CO2-mixture may allow significant streamlining of the process as well. Finally, CO2 soluble chelating agents have been used to extract toxic metals from acidic effluent such as that found in plating facilities.

Jan 1, 1999

By David R. Jessey

An ore microscopic and geochemical study of the nickel-cobalt occurrence in the Southeast Missouri Mining District has revealed several significant relationships. Siegenite [(Ni,Co)3S4] is the dominant nickel-cobalt sulfide in the ores, however, several other members of the thiospi¬nel group (AB2S4) occur: carrollite (CuCo2S4), nickelean carrollite [(Co,Ni,Cu)3S4], fletcherite [Cu(Ni,Co)2S4] and polydymite (Ni 3S4). In addition, bravoite [(Ni,Fe)S2], vaesite (NiS2), millerite (NiS) and gersdorffite (NiAsS) are present. Thiospinel composition varies dramatically within the district. Paragenetic studies have shown that the stratigraphically lowest thiospinels are the most cobalt-copper-rich. A detailed ore microscopic study of the AMAX Lead Company Buick mine has also shown significant changes in mineralogical association, texture and grain size of the siegenite along the north-south strike of the major ore bodies. Siegenite commonly replaces and veins chalcopyrite and is subsequently replaced by sphalerite. Less commonly, siegenite and chalcopyrite are observed to form linear replacements along sphalerite grain boundaries. The grain size of the siegenite varies markedly, but in a predictable north-south pattern that is consistent with a genetic model formulated from geo-chemical data. The compositional as well as textural trends displayed by the thiospinel mineralization could be exploited to optimize recovery of any or all thiospinels of economic interest.

Jan 1, 1981

By B. J. Jody

Each year, about 11 million tons of metals (ferrous and nonferrous) are recovered in the U.S. from about 10 million discarded automobiles. The recovered metals account for about 75% of the total weight of the discarded vehicles. The balance of the material or shredder residue, which amounts to about 3 million tons annually, is currently landfilled. The residue contains a diversity of potentially recyclable materials, including polyurethane foams, iron oxides, and certain thermoplastics. This paper discusses a process under development at Argonne National Laboratory to separate and recover the recyclable materials from this waste stream. The process consists essentially of two- stages. First, a physical separation is used to recover the foams and the metal oxides, followed by a chemical process to extract certain thermoplastics. The status of the technology is discussed, and the process economics are reviewed.

Jan 1, 1994

By Runsheng Xu, Haiyang Wang, Pengcheng Zhang, Tengfei Song

Semi coke, a byproduct in the chemical industry, is a new fuel for blast furnace injection in China. In this study, semi coke and bitumite were milled into different size, ranged from 0.147mm to under 0.074mm. The content of volatile matter and ash, which affect the combustibility of semi coke, were measured using muffle furnace. The mixture, in which the proportion of coal in different sizes changed, was blend by semi coke and bitumite with different size. Activation energy calculation and the comprehensive combustion characteristic index of all kinds of blends was also discussed. The result obtained by Thermogravimetry –Derivative Thermogravimetry curves indicates that the smaller the size of mixture is, the lower for the characteristic temperature, and the better for its combustibility, Semi coke can be a substitute for anthracite in blast furnace injection.

Jan 1, 2015

By Ray D. Peterson

The hydrothermal enrichment of chalcopyrite by CuSO, occurs in the absence of oxidizing or reducing reagants. Kinetics of the enrichment process were determined under autoclave conditions in the temperature range of 398°K (125°C) to 473°K (200°C). Covellite (CuS) formed first, followed by digenite (Cu,,,S), with rejection of iron to the solution. The kinetics have been explained by a model which includes diffusion during the first stage formation of covellite followed by surface reaction rate control when digenite be. The effects of particle size, temperature, pH, and cupric and ferrous ion concentrations on the leaching kinetics were examined. Additions of ferrous ion to solution markedly increased the rate of reaction.

Jan 1, 1994

By J. K. S. Tee

Using a novel method, zinc has been selectively removed from galvanized steel scrap on a laboratory scale. The separation is based on thermodynamic principles: during chlorination in air-chlorine (10:l) mixtures at 800 OC, zinc forms a volatile product (zinc chloride) while iron does not chlorinate as its oxides are more stable than the respective chlorides. As much as 92 % of zinc is removed from the surface of steel within 10 minutes. This process overcomes tedious and costly preparatory stages associated with leaching - electrowinning methods.

Jan 1, 1999

By T. K. Mukherjee, C. K. Gupta

"The importance of the processing of secondary resources such as solid industrial wastes and liquid effluents as well as byroducts for the recovery of the associated metal values hardly needs any elaboration. Such processing contributes in no small measure towards the augmentation of the availability and the supply position of resources. As an added benefit, it leads to a reduction in environmental pollution caused by the undesirable waste materials. As some typical examples of secondary resources in the Indian scenario, mention can be made of spent catalysts, metal/alloy scrap, ash, consumed batteries, flue dust, slag, sludge and slime, pickling solutions, spent acids, plating rinse solutions, spent etchants, waste water from synthetic fibre manufacture and from tanneries etc .. These wastes constitute a source of a variety of non ferrous metals. In the processing of secondary resources like these, the techniques of hydrometallurgy such as solvent extraction playa pivotal role.This paper outlines the efforts made to use solvent extraction to recover (1) base metals such as copper, zinc, nickel and cobalt from a number of secondary resources like cake, and sludge (2) refractory metals like molybdenum and vanadium from sulphidic byproducts and spent catalyst and (3) nuclear metal like uranium from phosphoric acid. In the case of base metals, process flowsheet involving the use of acidic extractants such as DEHPA and PC88A have been optimised. The problem of iron removal from the leach liquor, which influences the metal recovery process significantly, has drawn a special emphasis. In the case of refractory metals, basic extractants like Alarnine 336 has been pressed into service to produce kilogramme quantities of pure salts of molybdenum and vanadium. Finally, the paper gives a brief account of plant experience in recovering uranium from phosphoric acid, using a solvent system comosed of DEHPA and TOPO."

Jan 1, 1996

By Brian P. Atkin

The NISOMI-81 opaque mineral searcil and identification system uses quantitative color values (Pe, dA, y) and VHN as its determinative para-meters. The system is designed to operate on a Radio-Shack TRS-80 micro-computer which is interfaced to a motorised diffraction grating mono-chromator (WILSCAN). Using an interfaced monochromator/photometer combination a typical identification including the measurement of the photometer data on both specimen and standard, calculation of color values and a computer search takes about 6 minutes. The data file contains 240 minerals at present but can easily be expanded as reliable new data become available.

Jan 1, 1982

By P. R. Khangaonkar

The industry of tin ore mining, beneficiation and smelting gives rise to a number of waste products like the beneficiation plant wastes (called amang), tin smelting slags, refinery dross etc. Some of the wastes deserve treatment to obtain economically useful products or to recover the metal values. The paper describes studies conducted on two materials, viz., struverite-middling (struverite-magnetic tin), which is an intermediate product of beneficiation circuits of tin tailings, and tin-smelting slags. The struverite middling was studied for treatment by chlorination using carbon tetrachloride, so as to yield vapour products separable by convenient condensation. The treatment was also found to lead to a tin-rich product amenable for treatment by known hydrometallurgical routes. The tin smelting slag was studied by alkali-leaching so as to avoid any dissolution of iron and it was possible to obtain an iron-free product solution suitable for high purity tin recovery.

Jan 1, 1996

By Raymond E. Healy

Mercurian e1ectrum (Au-Ag-Hg alloy) is the principal Au-bearing phase in the massive sulphide ores at Trout Lake, Manitoba. The average composition of this phase (in wt %) is 49.2 % Ag. 38.7 % Au and 11.0 % Hg, with ranges of 17.34 to 76.47 % Ag, 1.62 to 79.86 % Au and 1.29 to 30.87 % Hg. Compositional variation reflects solid solution in the a-phase of the Ag-Au-Hg system. Backscatter electron imagery reveals systematic zoning and suggests a general crystallization sequence from metamorphic pore fluids of progressively Ag-rich compositions. Investigation of the occurrence of gold in mill products demonstrates that mercurian electrum accounts for over 90 % of the Au in Trout Lake ore. I Invisible" gold in pyrite (x = 0.72 ppm Au) and arsenopyrite (x 30.2 ppm Au) is confirmed by SIMS analyses, and accounts for 7-10 % of the Au in the ore, and 35 % of the Au lost to the tailings. The remaining 65 % of the Au lost to the tailings consists principally of mercurian electrum locked with pyrite. No significant losses of mercurian electrum in the size range amenable to flotation and/or regrinding is indicated.

Jan 1, 1989

By Tatsuzo Kitamura

The tank house of Tamano refinery, that started its operation in January, 1972, was constructed incorporating the application of Periodic Reverse Current (P.R.C.) from the outset of design works. In 1973, the production of electrolytic copper came up to 8,000 mtpm, a sharp increase ds compared with the designed capacity of 7,000 mtpm, and successful operation has been achieved up to the present. P.R.C. has been employed for the purpose of raising productivity level and reducing copper inventories. Since there were various problems in P.R.C. application to such a large sized cathode as 1 m x 1 m, special attentions were paid to the following items: -Development of a unique bus bar to make an electrolytic current to each electrode as uniform as possible. -Improvement of circulating method of electrolyte. -Application of high-performance equipment to realize a uniform spacing between anode and cathode. Owing to these creative technical developments mentioned above, technical level for operation up to 350 amp per sq m of cathode current density has been established. The quality of electrolytic copper, which was a matter of interest, has been proved to be as excellent as those of conventional electrolysis products through a long term supply to the field of SCR and Dip forming where high levels in quality are required.

Jan 1, 1976

By Levente Becze

The zinc bottom dross is obtained as a by-product from hot dip galvanizing operations and contains at least 92 % zinc, which is recycled mainly by pyrometallurgical processes. The overall costs of such a treatment, however, are often relatively high, and the very strict environmental protection regulations might also cause additional difficulties for the high temperature procedures in the future. Therefore, a novel hydro-electrometallurgical process has been developed in our laboratory, by which one can reclaim zinc of high purity, while attempting to achieve low energy consumption and making allowances for all the environmental restrictions. This aqueous processing technique, based on electrolytic refining in a cell equipped with anion-exchange membrane to separate the anode and cathode compartments, allows the indirect purification of the anolyte. Zinc is dissolved from the anode along with some of the impurity elements, while the intermetallic compounds (Fe-Zn, Fe-AI- Zn) are accumulated in the anode slime.

Jan 1, 2003

By Thomas M. Harris

To avoid the escalating cost of disposal of metals-containing wastewater and residues, new wastewater treatments will focus on the recovery of the metals. A combination of ion exchange and electrowinning can produce water suitable for discharge and relatively pure metals. The use of a chelating resin can enhance the selectivity of both the removal process and the elution of metals from the resin. A new, simple method of preparing a variety of chelating resins is being developed. The materials produced by this method exhibit interesting, as well as potentially useful, elution behavior. The performance of one test resin is described.

Jan 1, 1992

By Yoshinobu Fukumori, Testuya Watanabe, Futoshi Shikata, Hiroyuki Tokumitsu, Hideki Ichikawa, Masahito Miyamoto

Nano-particulate systems have attracted much attention recently in pharmaceutical field as drug carriers and functional components of pharmaceutical dosage forms. This paper describes our approaches in design and preparation of nano-particulate systems, including lipid nano-emulsions, chitosan nanoparticles and thermosensitive acrylic nanoparticles, for certain pharmaceutical applications mentioned below. The lipid nano-emulsions with their particle size smaller than 100 nm were prepared for gadolinium neutron-capture therapy (Gd-NCT) of cancer by a thin-film hydration method with sonication, and intraperitoneally injected into Greene's melanoma (melanotic No. 179)-bearing Syrian hamsters. This provided such a high gadolinium concentraton in tumor as 107 µg/g tumor (wet basis) at 48 h after administration. As an alternative gadolinium nano-carrier for Gd-NCT, biodegradable and highly gadopentetate-loaded chitosan nanoparticles (Gd-nanoCPs, 426 mTI in particle diameter and 9.3% in Gd content) were prepared by a novel emulsion-droplet coalescence technique. A significant tumor-killing effect could be obtained when Gd-nanoCP suspension was injected intratumorally twice 24 and 8 hours before neutron irradiation into B 16Fl O melanoma-bearing mice and subsequently thermalneutron was irradiated toward tumor site with a flux of 2 x 109 n/cm2/sec for 60 min. As one another application of nanoparticles, a novel acrylic composite latex with a hydrophobic core and a thermosenstively swellable shell was designed for fabricating microcapsules showing thermosensitive mode of drug release. The microcapsules with the composite latex-dispersing membranes exhibited an exceptionally rapid on-off response of drug-release in a thermosensitive manner.

Jan 1, 2000

By M. Nilmani, H. Pham

"A mathematical model was developed for the dissolution of particles in gas-stirred liquid baths, linking the hydrodynamic flow field of the bath, the average particle trajectory and liquid-side mass transfer controlled dissolution kinetics. The model was validated by comparison with experimental data for the dissolution rates of urea particles in gas-stirred aqueous CaCl2 solutions measured during this study. The dissolution rates of urea. particles were measured using an image analysis system.The effects of operating conditions on the dissolution rates of urea particles were investigated. It was found that the key operating parameters influencing the utilisation efficiency of particles were the gas flowrate, particle diameter and lance submergence. An optimisation of the operating conditions for the model urea-aqueous CaCl2 system indicated that the utilisation efficiency increased with decreasing gas flowrate and decreasing particle size for a given lance submergence.IntroductionThe utilisation solid reagents in molten baths varies from one process to another, depending upon the rates and mechanisms of the reactions between the particles and melts, as well as the trajectory and residence time of the particles in the melts. Previous studies have not attempted to predict the utilisation efficiency of injected solids by coupling the motion of the particle with its dissolution rate. Instead, the particles have usually been assumed to remain suspended in the bath until completely dissolved, and the mass transfer coefficients were based on the average specific mechanical energy dissipation rates in the bath. Investigations of this nature relevant to the present study have been undertaken by Apelian et al. [1], Brucato et al. [2] and Langberg and Nilmani[3]. The objective of the present study was to develop a mathematical model, incorporating both the reaction kinetics between the particles and liquid and the particle motion simultaneously, to predict the dissolution rates and times of the particles. The mathematical model was validated by comparison with experimental dissolution rates of a cold model analogue system measured using an image analysis technique, and then applied to optimise the operating conditions in the model system."

Jan 1, 1996

By Shoukun Wei, Cong Wang, Lin Cheng, Zhiyu Qiao, Jingkui Liang, Weidong Zhuang

"The subsolidus phase relations in the Sm2O3-CeO2-CuO ternary system sintered at 1000°C in air have been investigated by X-ray powder diffraction. The system can be divided into two ternary phase regions and three binary phase regions. Solid solution Sm2-xCexCuO4-y is the only ternary phase in the system. The maximum solid solubility was confirmed to be x = 0.2. The crystal structure, oxygen content and superconductivity of the solid solution Sm2-xCexCuO4-y have been investigated.I. INTRODUCTIONAfter the first discovery of the superconducting ceramic system La-Ba -Cu-O[l] with Tc = 30 to 40K, other families of cuprate-based ceramics have been synthesized with higher critical temperature. These oxides include the R-Ba-Cu-O (R: rare earth) systems (Tc=90K or so)[2,3], the Pb-Sr-(R,Ca)-Cu-O systems (T c = 50 to 100K), the Bi-Sr-Ca-Cu-O systems (Tc=80 to 105K)[4], the T1-Ba-Ca-Cu-O systems (Tc=85 to 125K)[5], the Hg-Ba-Ca-Cu-O systems (Tc=90 to 150K)[6,7], and some others. The improvement of Tc is very rapid. The measurement of the Hall and Seebeck coefficients shows that they all are p-type superconductors. In 1989, Tokura et al.[8] discovered the superconductors R2_XCexCU04_y(R = Nd, Pr, Sm) with Tc=20 to 24K (onset) and found that the charge carrier is electron in contrast to their hole doped counterparts. This discovery increases the fundamental understanding of the cuprate-based superconductors by comparing their characteristics and mechanisms to those of the p-type superconductors.One of the outstanding features of these n-type superconductors is the difficulty in obtaining samples in good charactors, such as the difficulty in obtaining zero resistivity state in single crystal or bulk samples; the semi-conductivity of bulk samples in ordinary state (opposite to the superconducting state) and a reducing reaction involved before the superconductivity has been found[9]. Therefore, it is necessary to optimize the sample preparation of the n-type superconductors. All the n-type superconductors have been found· considerable solid solubility. The compositional variations play a governing role in the carrier doping of the superconducting phases. Also, it is vital to the ceramic processing of superconductors to identify the compatible phases in the phase diagram. Finally, there is always the possibility of finding additional compounds, both superconducting and non-superconducting, in an unexplored system."

Jan 1, 1996

By Semih Perdahcioglu, Arthur E. Morris

"The curricula for the majority of Materials Science and Engineering programs is devoid of all but the most rudimentary coverage of the principles of material and energy balance calculations. As a result, graduated engineers that need to make such calculations are faced with three unpalatable options. First, attempt to learn the subject by attending workshops or short courses sponsored by corporations or industry groups. Second, outsource the needed work to a consulting engineering company. Third, purchase a software package that's capable of simulating a process. Each of these options require a considerable investment of employee time and effort. The first option might be the best if suitable computational software was readily available. We review the recent development of such software, which is entirely based in Excel. The software tools include a thermodynamic database, tools for multiple computations, and a flowsheet simulation program. These tools employ teaching by simulation.IntroductionPracticing engineers often come up with situations where they must learn a technical subject that they didn't cover in their college classes. One possibility is to obtain a couple of texts on the subject, and delve in. Or, they may sign up for an intensive short course where they can get personal instruction and guidance. But the first option requires a lot of study time, and the second option may not provide the specific instruction (or intensity of instruction) required to appropriately master the subject. Here we look at ways of using simulation techniques to learn the methodology for making material and energy balances on industrial processes.Industrial heating processes have undergone many changes over the past dozen years, as vendors have introduced new heating equipment designed to recover the greatest possible amount of heat from the fuel, and to meet stringent environmental challenges for emissions (especially NOx). Even though the recent unprecedented drop in price of natural gas may have altered the urgency for improving a plant's energy efficiency, the need is still there. Until recently, there was a dearth of readily-available software for process engineers to use for simulating a plant's flowsheet. The good news now is the existence of several Excel-based software tools that make the calculational process much easier. [ 1]. Plant engineers may also be interested in a DOEsponsored program[2] which allows plant-wide and ""what-if' analyses of the energy balance."

Jan 1, 2013