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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 Tetsuya Uda, Sakae Shirayama

"With the aim of producing nickel (Ni) metal directly from acidic aqueous solution containing cobalt (Co) and other impurities, selective reduction of Ni was examined. As a preliminary experiment, sodium hypophosphite monohydrate (NaH2PO2·H2O) was selected as a reductant, and reacted with aqueous solution containing 0.1 mol L-1 nickel sulfate (NiSO4·6H2O) and 0 ~ 0.05 mol L-1 cobalt sulfate (CoSO4·7H2O) for 3 hours at 90 °C. As a result, it was revealed that Ni was selectively reduced and separated from Co in the acidic region (pH= 4.8). In this study, differences of reduction behavior between Ni and Co were investigated, and the feasibility of Ni I Co separation by the selective reduction of Ni was discussed.IntroductionEfficient Ni condensation and separation from Co are essential in nickel hydrometallurgical processes. Currently, the hydrometallurgical production of Ni from oxide ore is mainly carried out by acid leaching at elevated temperature, followed by the removal of impurities using neutralization, and condensation of Ni and Co into intermediate products such as hydroxides and sulfides. Then, the intermediate product is dissolved in acid aqueous solutions, and Ni I Co separation is conducted by solvent extraction. Finally, Ni and Co are recovered by electro-winning. This complicated process consumes large amounts of alkali, hydrogen sulfide (H2S), and organic solution in a multiple-staged process'. To reduce the consumption of these chemicals, it is important to recover Ni more efficiently from acidic aqueous solution containing impurities."

Jan 1, 2014

By J. H. Huang

In this investigation, the selective precipitation of cobalt and molybdenum from Co-Mo aqueous solutions was studied in order to recover efficiently valuable elements from industrial effluents generated from a novel electrodeposition of nanocrystalline Co-based alloys process and reduce the effluent impact on environment. It was found that the behavior of cobalt in aqueous solutions was substantially affected by the presence of molybdenum. When adding 11.6 to 46.6g/L molybdenum to a 50g/L cobalt solution, the co-precipitation of molybdenum and cobalt started to occur at pH value of 3-4. However, without the presence of molybdenum, cobalt could only be precipitated out of the solution at about pH 6. Most of the molybdenum was found in the solid phase when the solution pH reached 5. After further increasing pH to greater than 7, the molybdenum dissolved back into the solution. Cobalt kept precipitating as the pH increased. When the pH was greater than 7, most of the cobalt was present in the solid phase. The chemical and physical characteristics of the precipitated materials were investigated by SEM, XRD, AAS and EDX. It was revealed that the precipitate was initially present as cobalt molybdate oxide hydrate and subsequently transformed as sodium cobalt molybdenum oxide. With further increasing the solution pH, the precipitate was transformed into cobalt hydroxide. Further investigation implied that most of molybdenum was chemically tied to the precipitate produced at the low pH, yet at the same time, physically entrapped at the high pH. The paper also presents the influence of reaction temperature and time on the precipitation process and kinetics.

Jan 1, 2003

By F. Ríos

Fundamental research, at laboratory scale, on the biomass adsorption capacity of a liquid mining effluent has been done. The biomass used corresponds to a Chilean seaweed called Gracilaria chilensis. The waste water effluent corresponds to clear water coming from thickeners of a Chilean copper mining operation. The biomass was dried, washed, treated with an acid solution, and then reduced in size. A characterization of Zeta potential was made, finding negative values in a wide pH range with a ZPC equal to 2.5 1. Adsorption tests were made- in an agitated system containing an artificial solution of CuS04 at a controlled temperature of 25 degrees Celsius; also, the effect of pH over the copper adsorbed was studied. Maximal adsorption of copper was found at pH equal to 6, and the Langmuir model indicated values for saturation of 52.08 mg/g and for standard free energy of about -21 KJ/mol. Kinetic adsorption was very high and fitted very well with a second order model equation, finding that 90 per cent of the adsorption occurred during the initial 10 minutes. After stoichiometric when 1 mol of copper is adsorbed, 2 mol hydrogen are released, showing that the main mechanism to remove heavy metals is the ionic exchange, and the seaweed ensures total discharge of copper adsorbed when the pH value is about 1. Experiments done with real waste water from thickeners lead us to conclude that optimal results for copper and molybdenum adsorption are at pH around 3.25 and the remaining treated water may be partially discharged into the water currents, thus showing that Gracilaria chilensis can be used to remove heavy metals easily from liquid effluents in the copper mining industry.

Jan 1, 1999

By A. V. Tarasov

The nonferrous metals industry has been a sector with one of the highest growth rates during the recent years. The prospects for the Russian metals industry during the period until 2010 are associated first of all with a growing domestic demand for its products. The technological level of the metallurgical operations in Russia is relatively low in comparison with industrially developed countries: the average energy requirement is higher by 20% to 30%; the amount of generated waste in the process of rolled products manufacture is twice as high; the average labor productivity is lower by 2.5 to 3.0 times; the overall negative environmental impact is twice as high. Improvement of the technological level of the nonferrous metals production under the conditions of market economy is possible by application of innovative technologies for the development of this sector. The main trends for development of the nonferrous metals sector are: - meeting of more stringent requirements to the quality of concentrates; - more complete recovery of associated elements as commercial-grade products; - development of continuous process lines based on autogenous, resource-saving and environmentally safe processes; - use of combined technologies, including pyrometallurgical, hydrometallurgical and upgrading processes; - expansion of the fields of application for nonferrous metals and their alloys.

Jan 1, 2006

By J. Brent Hiskey, Rebecca Grace Copp

The solvent extraction of yttrium and neodymium from copper pregnant leach solutions (PLS) using Primene JM-T, a primary aliphatic amine, has been studied. Effect of contact time, pH, sulfate concentration, and extractant concentration were investigated using synthetic and actual PLS systems. Standard experimental conditions were 5 minute contact time, pH ~2.5, and 10 % v/v Primene JM-T concentration. Distribution isotherms were constructed for the pure systems and for actual copper leach solutions. Synthetic solutions contained 100 ppm Y and ~75 ppm Nd. Samples of PLS contained 2 - 10 ppm Nd and 14 - 30 ppm Y. Results showed that complete extraction of both yttrium and neodymium occurred within five minutes and at pH values greater than 1. It was also found that sulfate concentration does not inhibit extraction at any concentration. Additionally, the distribution isotherms created show that extraction for these metals can operationally take place in one stage.

Jan 1, 2016

By Lei Zhang, Shining Chen, Lina Wang, Pu Liu, Benquan Fu, Jiannyang Hwang

A three-dimensional (3D) electrode reactor combined with Fenton reagent was used for advanced treatment of coking wastewater from secondary biological treatment. Effects of some key factors on total organic carbon (TOC) removal rate were investigated, and the results were compared with those of the common three-dimensional electrode reactor. Experimental results showed that TOC removal rate could reach 51.7%, when optimal operating conditions were as follows: initial pH value 3.5, H2O2 dosage 17.6mmol/L, reaction time 90min and FeSO4·7H2O dosage 3.5mmol/L. Analytical results from UV absorption spectra indicated that the organic substances in the coking wastewater were well degraded by this system, which provided good experimental basis for the practical application of this process in the treatment of coking wastewater. This can be meaningful for the treatment of other kinds of wastewater.

Jan 1, 2015

By Thomas K. Chow

For the well-being of all living creatures and in response to green-environment policy from governments around the global, it is essential to reduce SO2 emissions from mining / smelters as well as other industrial facilities around the globe. However, often times, these SO2 containing flue gases and smelter flash gases also include oxygen and SO3, which complicate the SO2 removal process and technology. There are many novel technologies recently developed for removing SO2 from such gases. Most of these, however, have not yet commercially demonstrated that they are technically viable and economically feasible. Many of these novel processes also generate undesired byproducts, which themselves then need to be disposed of in a safe and cost effective manner. Fluor has developed the Fluor SOx Cleanup Process with a wide variety of process configurations to customize removal of the undesired flue gas constituents in a cost-effective manner. The process removes practically all SO2 in the form of salable elemental sulfur and also reduces CO emissions. Successful operation of major components of the Fluor SOx removal technologies has been demonstrated in many commercially operating units. Besides their technical viability and economic feasibility, Fluor SOx removal technologies do not generate any undesired byproducts or encounter SO2 associated corrosion issues. Moreover, these technologies produce high-purity, saleable elemental sulfur. This paper discusses the merits of the Fluor SOx removal technologies, their technical and cost advantages, their simplicity in design and operation, and their readiness for implementation.

Jan 1, 2006

By V. Blet

Rare earth elements (REE) are regarded today as highly critical raw materials but currently lack suitable recycling processes. A combined hydro- and pyrometallurgical process aimed at REE recovery from used NdFeB permanent magnets was recently developed by the CEA. The process integrates the physico-chemical treatment of magnets, followed by a solvent extraction step for the recovery and intra-REE separation using a selective extractant. A subsequent pyrometallurgical treatment via molten chloride salt electrolysis allowed the isolation of pure Dy metal. Technical-economic assessment and life-cycle analysis were also conducted. Following this first successful demonstration, a new project aimed at the recovery of REE from end-of-life nickel-metal-hydride batteries is currently being developed in association with industrial and academic partners. The project aims at evaluating from an experimental and economic perspective different processes converging at the production of value-added products such as cermet materials for catalytic applications, purified REO concentrates, or metallic alloys.

By Masanori Harata

A fundamental study was conducted on a new process for producing scandium (Sc) metal or aluminum-scandium (Al-Sc) alloy by the calciothermic reduction of scandium oxide (Sc2O3). In this study, aluminum (Al) and calcium chloride (CaCl2) were used as the collector metal and flux for the reduction, respectively. A mixture of Sc2O3, Al, and CaCl2 in a tantalum crucible was placed inside a stainless steel reaction container, and the feed mixture was reacted with calcium (Ca) vapor at 1273 K for 6 h. After the reduction experiment, the reaction product (CaO), CaCl2 flux, and excess Ca reductant were removed from the obtained alloy sample by leaching with an aqueous solution. The formation of Al3Sc in the Al matrix phase of the alloy was confirmed by X-ray diffraction (XRD) and electron microprobe analysis (EPMA). This result indicates that Sc2O3 was successfully reduced to metallic Sc and alloyed in situ to form liquid Al-Sc alloy during the reduction. When Al was not used in the reduction experiment, a complex oxide (CaSc2O4) was formed, and the reduction was incomplete. This study demonstrates that the Al-Sc alloy can be directly produced by calciothermic reduction using CaCl2 flux and Al collector metal.

Jan 1, 2006

By John W. Lund

The Geo-Heat Center has been investigating the utilization of waste silica from the Cerro Prieto geothermal field for several years. The main objectives of the research were to com-bine silica with various additives to (1) form bricks for low cost housing, and (2) to produce a suitable road surfacing material. The various additives that were tested included hydrated lime, portland cement, plastic fibers, asphalt cement and emulsified asphalt. The silica-cement combination produced the strongest bricks and had the best weather resistance, whereas, the silica-lime combination produced the bricks with the lowest thermal conductivity and specific gravity density. The addition of plastic fibers to the silica-lime mixture improved both strength and weather resistance. The combination of asphalt and silica is not suitable as a road surfacing material, however, silica-cement appears promising.

Jan 1, 2006

By I. U. Onyenanu, C. E. Ilochonwu, E. I. Nwonye, C. O. Nwajagu

This work shows how pure silica was derived directly from rice husks ash (RHA) in different temperatures for reduction to Silicon (Si). The processes to form Si materials are usually complex, costly and energy-intensive. The silica in the ash undergoes structural transformations depending on the conditions of combustion. A high purity silica was produced at 650oC after burning the rice husk (RH) for up to 7 hours. The purity of the silica was determined by dissolving the RHA with alkali solution to form sodium silicate solution of pH 11.0. This was added to hydrochloric acid of pH 1.5 which lowered the pH of the solution to 4.0 to form silica gels. The silica gels produced were washed and dried to powder and then characterized using XRD and EDX techniques. This study was done to reduce energy waste and environmental pollution in Nigeria as silica is used to develop many materials.

Jan 1, 2015

By Abhishek Lahiri

Titanium dioxide is extracted from titaniferous ores by chloride and sulfate processes. These two processes produce wastes in the forms of iron chloride, iron sulfate and rare earth oxides gangue, each of which has to go through a further treatment before it can be disposed safely, which may be expensive. The shortage of high-grade ores is also making the two conventional processes less efficient. In view of the above mentioned problems, an alternate beneficiation process of roasting titaniferous ores with soda ash is discussed. The advantage of this process is that, there is no production of wastes. The impurities present in the ore can be selectively separated after the roasting process. The roasting of titaniferous ores with soda ash was carried out between temperatures of 873K and1173K for several hours. The roasting process resulted in the formation of complex alkali compounds and various sodium titanate compounds, depending on the Na2CO3to ore ratio. The phases formed after roasting were characterized using the X-ray powder diffraction (XRD), X-ray florescence (XRF) and scanning electron microscopy (SEM) techniques. The phase equilibria in the Na-Ti-O system are evaluated and compared with the phases obtained after the roasting process. The effects of temperature and the proportion of sodium carbonate on titaniferous ores are also discussed. From the experimental data, the overall reaction kinetics and phases formed were analyzed to ascertain the mechanism of overall reaction and the rate-limiting steps.

Jan 1, 2006

By Alexandre Bonan

The paper reports on the results of a kinetic study on the oxidation reaction of aqueous free cyanide ions with H202, in the presence of Cu(2+) catalyst. The variables and respective ranges studied were the following: (CN) ° = 10 -100 mg/l pH = 10 -11 (H202/CN) mol ratio = 1 -3 (Cu/CN) mol ratio = 0 -0.25 The results lead to the development of a semi-empirical model whish incorporates both the useful oxidation reaction and the parallel alkaline decomposition of H202.

Jan 1, 1992

By Eltefat Ahmadi

Iron-free titanium oxycarbonitride (TiOxCyNz) is a promising feedstock for production of titanium tetrachloride (TiCl4) at low temperatures. In this study, the effects of leaching variables such as temperature, time, particle size of staring material and concentration of the leaching solutions were evaluated on iron removal from nitrided Malaysian ilmenite by Becher process. The nitrided ilmenite was prepared by isothermal reduction with graphite at 1200 °C for 3 h in H2-N2 atmosphere. The aerated leaching experiments were conducted at 50–90 °C with addition of 0.3–2.0 wt% of NH4Cl catalyst. The highest extent of iron removal (XFe) was obtained at about 96.2% for the sample leached at 90 °C for 7 h with 2.0 wt% NH4Cl. The iron concentrate and titanium oxycarbonitride product were characterized by ICP-OES, XRD, XRF and SEM-EDX analyses. The results indicated that the aeration leaching process was a successful route to prepare low-iron titanium oxycarbonitride.

By S. Goto, S. Yamashita, K. Hata

"The average consumption of zinc dust for purification of zinc leaching solution is more than 25 kg per tonne of electrolytic zinc. Authors proposed to remove impurities in zinc leaching solution by electrolysis instead of cementation by zinc dust. The effects of copper and arsenic on electrodeposition of cobalt in zinc sulfate solution were examined fundamentally using a potentiostat. It is observed that cobalt is easily deposited on a cathode at potentials under -480mV with arsenic. Mesh cathodes of stainless steel and lead anodes were used in a small electrolytic cell and the electrolyte was circulated through 'the electrodes during the electrolysis. The effect of electrolyte circulating rate , pH, cell temperature, current density, and concentration of copper and arsenious ions on removal of cobalt were studied. Removal of Cd and Ni are also examined.IntroductionCobalt is difficult to remove from a zinc leaching solution by a simple cementation reaction using zinc dust. However, it is easily precipitated by zinc dust with co-addition of arsenious or stibinous oxide and copper ion in practical operations(I), (2), (3). The consumption of zinc dust for purification is 16-152 kg per tonne of electrolytic zinc and 65% of this zinc dust consumption is used for cobalt purification. The average retention time for purification of cobalt is 4.5 hours (1). A more economical process for purification is desired instead of zinc dust. The mechanism of this acceleration effect of copper and arsenious oxide on removal of cobalt are explained by the authorsas follows; a galvanic cell is formed between zinc dust and copper which is precipitated firstly, and cobalt is reduced on copper as Co-As alloy by this galvanic current(2). This assumption was confirmed in experiments using a galvanic cell with a membrane( 4). The following galvanic reactions occur between zinc dust and copper precipitate; on copper cathode,2H+ + 2e -= Hz(g)2Coz+ + 2HAs02 + 6H ++ 10e -= 2CoAs + 4HzOand on zinc anode,Zn = Zn = 2+ 2e –This galvanic current becomes almost zero in a zinc sulfate solution which includes only cobalt and no arsenious oxide, and cobalt is weakly deposited on a copper cathode. Cobalt deposition requiers a high degree of cathodic polarization. However, the galvanic current flows almost constantly in an electrolyte, which includes arsenious oxide, and the cathode potential is kept at about -500mV. Cobalt is precipitated as Co-As on the cathode.The authors assumed that cobalt may be removed by electrolysis at a very low current density instead of zinc dust and the following experiments were carried out. In the first part of this paper, the fundamental experiments using a potentiostat on the behaviour of cobalt in zinc sulfate solution are described. In the second part, the results of the electrolysis are reported. Cobalt is removed by a new type of an electrolytic cell, which was desigoed to <Iccelerate the rate of deposition of cobalt. The removal of cadmium and nickel in a solution which includes cobalt and arsenic are also examined."

Jan 1, 1997

By Li Fangi

This paper describes the characteristics and regularities of a process to recover rare earth minerals from Baotou Ore with H-205 collector. H-205 is a kind of hydroxamic acid with amide as a polar group and poly-cycle aromatic hydrocarbon as a non-polar group, having strong ability to capture RE minerals (bastnasite, monazite). When adding a certain dosage of water glass and some other modifying agents, and maintaining pH value between 8.5 and 9.5, RE minerals can be effectively separated from calcium and barium minerals, such as fluorite and barite, etc. Under normal flotation temperature and concentration, when using H-205 to float RE minerals, it needs a bit longer conditioning time (a few minutes longer than that for the conventional collectors). It is also shown that the reagent has the property of resistance to hard water. The laboratory scale and pilot scale tests of the process have been carried out on bulk froth containing RE minerals and fluorite taken from Ore Dressing Plant of Baotou Iron and Steel Company, in both cases, high grade RE concentrates were obtained and the recovery increased remarkably. Therefore, the process has a great practical value.

Jan 1, 1989

By Peter G. Smith

Tri-calcium aluminate (TCA) is a dominant alkaline component of the red mud residue from the Bayer process. A method being considered for industrial implementation partially neutralizes the residue by contacting it with gaseous CO2. This paper outlines the chemistry of CO2neutralisation of TCA under conditions relevant to the treatment of Bayer residue. CO2 neutralisation of the liquor is fast. It results in the formation of amorphous aluminium hydroxide and dawsonite that agglomerate together. Neutralisation of solid TCA is slower and leads to the formation of calcite, dawsonite and amorphous aluminium hydroxide. The dissolution of TCA in partially neutralised slurries causes pH reversion. However the carbonated solutions contain a store of bicarbonate that can supply aqueous carbon dioxide to complete the transformation. The pH at which the carbonation is carried out will affect the degree of TCA transformation during the carbonation process. In particular, if the pH of the carbonation is too low (near 7.0), calcite precipitation is inhibited and the degree of transformation is low. Controlling the carbonation pH helps to optimise the neutralisation process.

Jan 1, 2003

By Wentao Guo, Xuefeng She, Qingguo Xue, Jingsong Wang

By the coke gasified reaction device and online measurement high-temperature compressive strength apparatus, the variation of pore structures of coke after gasified reaction with CO2 and H2O was investigated. Research illuminating the influences of solution loss rate, temperature, and carbon species on compressive strength of coke was also carried out. The results showed that the total compressive strength was higher than for the reaction with CO2. The high-temperature compressive strength of coke decreased with the increasing of solution loss ratio or temperature after reacting with CO2 and H2O. At the same solution loss ratio, the damage of pore structure to coke strength after gasified reaction with H2O was relatively smaller and the deformation resistance was stronger when compared with that in CO2.

Jan 1, 2016

By Suguru Kohno, Yoshihiro Momose, Masakazu Honma, Tokirou Kamosawa

Copper metal surfaces have been examined by an extremely sensitive surface analysis technique called temperature programmed photoelectron emission (TPPE). The surfaces were ultrasonically cleaned and subsequently abraded by a screw in organic solvents and water. The TPPE apparatus is composed of a Geiger counter with Q gas (He+ iso-C4H10). The curve of photoelectron emission (PE) intensity vs. wavelength from 300 to 170 nm, termed PE spectrum, was repeatedly measured at different temperatures in the temperature- increase process from 25 to 350°C. The number of emitted electrons in a PE spectrum (PE total count) increased, reached a maximum at-250°C, and decreased with increasing temperature. With the surfaces cleaned alone in the liquids the maximum PE total count decreased in the order C3H70H > (CH3) 2CHOH > C2HpH > CHPH > H2O. With the mechanically abraded surfaces in the liquids the maximum PE total count changed as a function of the abrasion period and the maximum tended to appear at higher temperature with increasing abrasion period; the maximum value at 10-min abrasion decreased in the order H2O > CHpH > C2HPH > (CH3) 2CHOH > n-C3HpH. It was suggested that the TPPE behavior can be related to the acid-base interaction between the alcohols and the abraded metal surfaces and the presence of a contaminant over layer on the surface. From the XPS analysis of the 01 s spectra it was suggested that the chemical change of the adsorbed oxygen to oxide oxygen with temperature plays a substantial role in the appearance of the maximum PE total count.

Jan 1, 2000