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By Katsutoshi Inoue

The sulfuric acid leaching of spent hydrodesulfurization catalysts yields an acidic solution rich in rare metals such as molybdenum, vanadium, cobalt, and nickel in addition to aluminum. For the purpose of separating and recovering the rare metals from the solution, basic solvent extraction characteristics of the metals involved with commercially available acidic organophosphorus reagents like TR-83, PC-88A, PIA-8 and CYANEX 272 as well as aliphatic alpha-hydroxyoxime LIX 63 from sulfuric acid media were investigated in the present work. It was demonstrated that CYANEX 272, PIA-8 and LIX 63 possessed excellent selectivity for molybdenum and vanadium over the other metals at comparatively low pH. Further, recovery of molybdenum and vanadium from the total leach liquor by the selected extractants was discussed. Additionally, in order to achieve preferential separation and recovery of cobalt and nickel over an appreciable amount of aluminum from the raffinate obtained after recovering molybdenum and vanadium, a systematic investigation was conducted on synergistic extraction behaviors of the mixed solvents of LIX 63 in combination with a series of acidic extractants such as CYANEX 272, PIA-8, PC-88A, D2EHPA, TR-83 and OPEHPA for cobalt, nickel and aluminum. It was elucidated that all of these mixtures could exhibit a good synergistic effect for extraction of cobalt and nickel, and that the lower the pKa of the acidic extractants, the greater the synergism. Contrarily, the extraction of aluminum, was considerably suppressed by LIX 63. Effective extraction of cobalt and nickel away from aluminum was accomplished from the sulfate solution at low pH (1.0 - 2.5) with the mixtures. In particular, the mixtures consisting of LIX 63 and CYANEX 272 or PIA-8 appeared to be the most feasible and economic from an industrial point of view, yielding acceptable separation efficiency for cobalt and nickel over aluminum and .a low acidity requirement for stripping cobalt and nickel as well as negligible degradation of LIX 63. Aluminum can be readily recovered as sulfate salt from the raffinate obtained after recovering molybdenum, vanadium, cobalt and nickel as outlined above by conventional crystallization method.

Jan 1, 1995

By E. Maziar Sauber

In order to prepare a more desirable feedstock for a rare earth elements separation refinery, cerium, a penalty element in the refinery feedstock, should be removed from the mixed rare earth elements oxide or carbonate feedstock. In this study, cerium (III) to cerium (IV) oxidation by calcium hypochlorite and subsequent precipitation was used to remove cerium from a mixed rare earth elements chloride solution. A factorial design of experiments was used to determine the effect of process variables such as temperature, pH, and oxidizer addition on the oxidation of cerium (III) using synthetic solutions. Under certain test conditions, all of the cerium was successfully removed from the chloride solution, and some REE accompanied cerium and reported to the precipitate. This proposed technology can allow for low cost removal of cerium from mixed rare earth elements chlorides.

By Minji Jun

Leaching of the surface-coated metals from waste acrylonitrile butadiene styrene plastics (WABSP) has been investigated in the ammoniacal solution. The ammoniacal leaching of WABSP (typically containing 4.1 wt% Cu, 1.3 wt% Ni, 0.03 wt% Cr) efficiently dissolved copper and nickel, leaving unleached chromium as fine particles. The results indicate that the anions of different buffer media for metals leaching follow the order: CO3 2− > Cl− > SO4 2−. A declined leaching with high NH4OH–(NH4)2CO3 ratio (8:1) and a steep rise in extraction with high pulp in solution revealed the influence of anion (CO3 2−) and cation (Cu2+) present in the system. The leaching performed in carbonate solution by maintaining 5.0 M total NH3 concentration as NH4OH–(NH4)2CO3 ratio, 4:1; pulp density, 200 g/L; agitation speed, 400 rpm; temperature, 20 °C and time, 120 min yielded the maximum extraction (>99%) of copper and nickel. The study reveals a plausible recovery of the surface-coated metals from the WABSP without altering the properties of polymer material that can be recycled separatel

By Richard D. Hagni

Polished sections of pyrometallurgical intermediate products from a simulated commercial flash furnace were examined by reflected light microscopy, scanning electron microscopy-energy dispersive spectrometry and electron backscatter analysis, and microprobe analysis for phase and textural relationships. The smelter feed is a copper concentrate from a porphyry copper deposit. The concentrate consists primarily of chalcopyrite, bornite and pyrite with smaller amounts of covellite, chalcocite, molybdenite, magnetite, galena, and sphalerite. The flash furnace reactions for pyrite and chalcopyrite can be observed by reflected light microscopy. Reacted angular particles of pyrite exhibit successive rims of fibrous pyrrhotite and hematite or magnetite. Reacted angular chalcopyrite particles show successive rims of bornite, digenite, and chalcocite. Spherical particles, formed by the complete melting of former pyrite particles, consist of variable amounts of granular pyrrhotite with magnetite rims and minor hematite. Spherical particles, formed by the complete melting of former chalcopyrite particles, exhibit exsolution intergrowths with varying proportions of intermediate solid solution, bornite, digenite, and chalcocite and have rims of hematite, magnetite, and copper-iron spinel. Sphalerite and molybdenite do not show evident mineralogical reactions.

Jan 1, 1987

By Francisco M. S. Garrido, Fabiano A. C. M. Passos, Carla N. Barbato, Karoline K. Ferreira, Danielle C. Castro, Adriana A. S. Felix, Luiz C. Bertolino, Fernanda A. N. G. Silva, Karla M. A. Simões

Cancrinite and sodalite are characterized by high capacity of adsorption due to its porous structure. The aim of this work was to use kaolin from Borborema-Seridó/Brazil as a source of aluminium and silicon to hydrothermal synthesis of sodalite and cancrinite and to evaluate the best conditions to the formation of these phases. Therefore, kaolin was heated at 700 and 900 °C for 2 h in order to transform kaolinite in metakaolin. Thereafter, experiments with the calcined kaolin’s were carried out between 150 and 230 °C for 30–270 min on a stainless steel pressure vessel using NaOH, Na2CO3 and H2O. The samples were characterized by X-ray diffraction, nuclear magnetic resonance, scanning electronic microscopy, thermogravimetry, and Zeta potential. The most pure sodalite phase was obtained at 230 °C, with the kaolin/NaOH ratio of 1:1, low concentration of Na2CO3 and smaller time of synthesis (30 min). On the other hand, for the synthesis of cancrinite phase at 230 °C, it was necessary to use kaolin heated at 900 °C, a longer time of synthesis (270 min) and a higher concentration of Na2CO3.

Mar 1, 2017

By C. P. Snyman

Three independent methods of coal classification can be distinguished, namely on the basis of grade, type and rank. The latter two can be determined accurately and unambiguously only by means of microscopical techniques. These three independent variables affect all the coal properties and therefore also the technological behaviour of a particular coal. The influence of the inorganic constituents of coal on the fusibility of the ash and on the length of the slag, and also on fouling and slagging, is discussed. The fractionation of the ash-forming constituents during combustion and gasification of pulverised coal shows that fouling and slagging are not related directly to the fusibility and composition of ash of the coal as a whole. The results of combustion experiments using a drop furnace technique indicate that the ignition temperatures of the light volatiles in the coal, and of the formed char, as well as the burn-out time of the char are more dependent on the rank than on the type or grade of the original coal. High-ash coals, however, apparently ignite at lower temperatures and are more reactive than low-ash coals of similar type and rank. The surface properties of coal, which are important in froth flotation and oil agglomeration, correlate well with the inherent moisture content (and by inference with the heat of wetting and the calorific value) and therefore with the type and rank of the coal. In coal exploration, variations of rank offer the possibility of predicting the presence of an intrusion near the seam, thus contributing to more effective exploration and mine planning.

Jan 1, 1991

By Zhang Hengzhong

Based on thermodynamics of surfaces and a proposed two-dimensional state equation for surfaces, the relationship between the surface tension (Y) of a solution and the activity (a1) of its component (i) was derived: (1/Y)r2-.¬E (ai/Yl) The derived equation was verified with reported experimental data of water-alcohol systems and water-acetone system, the calculated results showed astonishing coincidence with experimental. Applications of the equation to the five matte systems Cu2S-FeS, Ni3S2-FeS, FeS-PbS, Cu2S-PbS and FeS-Cu22S-PbS also demonstrated that at given matte compositions the calculated surface tensions agreed with experimental fairy well.

Jan 1, 1993

By M. Bugdayci, Onuralp Yucel, K. C. Tasyurek

This paper is a contribution to the theory and quantitative understanding of the processes for the production of magnesium, calcium and strontium metals by metallothermic process. In the present study, effect of reductant type was investigated. Thermodynamic simulation of system was made by Fact Sage 6.4 program. In order to produce magnesium metal, effects of reductants “FeSi, Al, Si and CaC2” were investigated. To understand Calcium-oxide reduction system, effects of Al and CaF2 addition were investigated for different temperatures. In the last simulations, SrO reduction parameters were simulated. Al used as main reductant and BaO, CaO, CaC2 were added to green mixture as a functional additive. Finally probable phases and minimum reduction temperatures are determined.

Mar 1, 2018

By N. Kanari

The kinetics of oxychlorination of MgO by Cl2+O2 was studied in the temperature range of 850 °C - 1025 °C, using thermogravimetric analysis. The effects of C12/02 ratio, gas velocity, temperature and partial pressure of reactive gases on the reaction rate were investigated. The oxychlorination process was characterized by an apparent activation energy of about 214 kJ/mol. The reaction orders with respect to C12+O2. C12 and O2 at 950 °C were about 0.65.0.98, and -0.37, respectively. Some data about oxychlorination kinetics of MgO, Cr2O3, and MgCr2O4 contained in chromite were compared. Efficiency of using oxychlorination for the removal of iron oxides contained in magnesia was demonstrated.

Jan 1, 1999

By Bora Derin

This work deals with the recovery of valuable metals from the ancient copper smelting slags located in Küre-Turkey. In this process, copper and cobalt were recovered in metallic form and/or as their compounds, whereas iron was recovered as magnetic oxide or pigment. Abrasive grit material was produced using reduced final slag. The process stages involved carbothermal reduction in a DC arc furnace, granulation, leaching, chemical precipitation, selective sulfidizing roasting and product preparations. In this paper, the process stages were described as theoretically and experimentally whereas slag and products were characterized in detail.

Jan 1, 2003

By J. S. Pitsillos

A new furnace tapping technique involving the simulation of a control valve at the exit to a furnace is being investigated. The purpose of this new tapping technique is to regulate the flowrate of liquid furnace products( slags, metals and mattes). Numerical modelling and experimental work has been carried out on tapping of slags leaving a SIROSMELT reactor and the results found to be in good agreement. Numerical modelling has also enabled prediction of the important industrial conditions for the onset of blockage from the shape of the pressure versus flowrate curves. Slag launder experiments have been carried out and a one-dimensional heat transfer model was used to evaluate the effectiveness of launder covers and different coolants. From the experimental results and mathematical model some launder design guidelines such as inclination angle, covers and coolants have been developed.

Jan 1, 1991

By Musa Karakus

In an attempt to explain the phenomena of lead entrainment during Cu drossing of lead bullion, two different synthetic lead bullions were heated to 1050°C, cooled slowly to various temperatures, and then quenched. The morphology and composition of dross particles that form when Mn is used to desulphurize bullion also were examined. Polished sections of these pyrometallurgical products were examined by process mineralogical techniques to identify the impurity phases, determine their chemical compositions, examine the morphology of the impurity phases and evaluate the potential for lead entrainment in such crystals, and characterize pre-quench and quench-generated phases. The phases crystallized were metallic lead, metallic copper, galena, chalcocite, albandite, Cu14.4Pb2S9. and 5.5Pb2S3.5. Metallic copper formed isometric skeletal crystals, chalcocite formed platy and skeletal crystals, and 1formed crystals and eutectic intergrowth with chalcocite and Cu14.4Pb2S9 or Cu5.5Ph2S3.5. The pre-quench crystals are larger and usually exhibit skeletal forms; the quench-generated phases are only a few micrometers across and disseminated throughout the lead matrix. Skeletal crystals of metallic copper and chalcocite form three dimensional networks that entrain large amounts of metallic lead.

Jan 1, 1989

By J. Grogan

Leaching of galvanized steel coatings allows the steel substrate to be used as a zinc-free scrap source to steel and iron furnaces. In this study the behaviors of sulfuric acid leaching solutions are investigated. The ranked significance of the variables are shown to be acid concentration > temperature > zinc concentration. Examination of the leaching mechanism finds the rate-limiting step to be the cathodic hydrogen reduction reaction. This rate is not only influenced by acid concentration, but also by the hydrogen reduction exchange current density. Dezincing leaching rates are improved by taking advantage of the higher exchange current density of the iron substrate versus the zinc coating. This is accomplished in practice by increasing the exposed interfacial zinc:iron surface area through shredding. Also, a leach control mechanism is proposed through online monitoring of the zinc-iron couple mixed potential.

By H. Matsuda, T. Iwashita, H. Awata, H. Liwei, D. Hirabayashi, Y. Saito, S. Ozawa, Y. Goto

"The present study is concerned with investigating the effect of chemical treatment on enhancing the HCl absorption capacities of coal burnt ash and slag. It was found that the HCl absorption capacity of coal burnt ash discharged from fluidized bed combustor was improved by hydration with water and 5% polyethylene glycol solution. This phenomenon was based on an increase of the specific surface area of treated coal burnt ash. The HCl absorption capacity of hydrated ash with polyethylene glycol solution was almost equivalent to that of standard CaO and Ca(OH)2. In particular, the specific surface area of hydrated ash with polyethylene glycol solution was found to be 19 m2/g, which was more than over eight times larger than that of raw sample. Hydrated slag treated with lON sodium hydroxide solution also showed high HCl absorption capacity, with highly improved surface area. It was found that the absorption capacity of slag for HCl depended on the treatment time, showing the maximum absorption capacity for 12 hours of hydration treatment.IntroductionA large amount of coal burnt ash, slag and dust are discharged from such industrial processes as coal combustion and metal refinery etc., and it becomes an serious problem to recover and diminish these solid wastes because of the shortage of dump sites and subsequent metal elution to the environment. Figure 1 shows the present situation of reutilization of coal burnt ash and slag in Japan [1,2]. It is shown in this figure that these solid wastes are recycled as materials in the fields of earthwork, agriculture and forestry etc. A part of these solid wastes, however, is still dumped to landfill. To decrease this dumped amount, the development of environmentally friendly reutilization technique for these solid wastes is of great importance."

Jan 1, 2000

By R. Steven Izatt

Green chemistry principles will be discussed, and examples will be given of the use of Molecular Recognition Technology (MRT) to selectively separate specialty metals such as cobalt, nickel, bismuth, rhenium, molybdenum, indium and germanium from various primary and secondary feed streams. Recovery of these metals has numerous advantages including (i) conservation of valuable resources, (ii) prevention of environmental damage, and (iii) elimination of capital and operating expenses due to re-processing or disposal of metal-bearing streams.

By S. E. Khalafalla

A method for preparing ferrochromium alloys containing less than 2 pct carbon has been devised in a single vacuum furnace reactor. This method can conserve chromium and should reduce the capital and energy requirements relative to chromite electrothermal reduction. Reduced products containing less than 2 and as low as 0.01 wt pct carbon were obtained by reacting pellets of chromite and carbonaceous reductant mixtures at pressures of 0.1 to 1 ton and temperatures of 1,230° to 1,320° C. The extent of reduction increased with increased temperature and decreased pressure; however, operating conditions were limited due to the onset of significant chromium vaporization at higher temperatures and lower pressures. Foundry coke, anthracite, and carbon black were found to be superior to graphite as reductants. The reduction of chromite to metallics was found to proceed via the carbide intermediates Fe3C or Cr3C2. Lime accelerates the. rate of solid state reduction of chromite and can shorten the furnacin1r time at 1,3000 C under vacuum from 13 hours to less than three hours. Additional lime and silica are added to the hot reduced chromite after releasing the vacuum and raising the furnace. temperature to 1, 700° C. Soaking the charge for about 20 minutes gave a button of low carbon ferrochromium alloy beneath a well-defined slag layer.

Jan 1, 1985

By KNona C. Liddell

The ion interaction model Pitzer proposed twenty years ago is today the most widely used method for calculation of osmotic coefficients and electrolyte and single ion activity coefficients in aqueous solutions. This is due in part to the accuracy of the results that have been obtained for many concentrated electrolytes. An additional factor is that, compared to alternative activity coefficient models, there are many more parameter values available for the Pitzer equations. The important features of this model are reviewed. Published parameter values for Co, Ni, Cu, Zn and Fe are tabulated, and applications of interest in the aqueous processing of these metals are described.

Jan 1, 1993

By Yiling Zhang, Paul A. Salvador, Gregory S. Rohrer

"Photocatalysis utilizes solar energy to produce hydrogen by splitting H2O. When a thin film of photocatalyst TiO2 is supported on a ferroelectric BiFeO3 substrate (band gap ~2.5 eV), the TiO2/BiFeO3 heterostructure is capable of photochemically reducing Ag+ to Ag0 in aqueous solutions under blue light with enhanced efficiency. The observation of spatially selective silver patterns on surface of the heterostructure after reaction suggests that photogenerated electrons and holes in ferroelectric BiFeO3 are driven in opposite directions to reduce their chance of recombination. Comparisons of the amounts of reduced silver on TiO2 film grains with distinct phases/orientations show that the reactivity is mildly preferential on anatase TiO2 phase and does not strongly depend on crystallographic orientation of BiFeO3.IntroductionTitania (TiO2) is capable of photocatalytically converting H2O to hydrogen and oxygen under the irradiation of ultraviolet light. [1, 2] One of the limiting factors for titania to be used as an effective photocatalyst is its band gap. Because the absorption edges of rutile and anatase titania are at 3.0 eV and 3.2 eV, respectively, they can only absorb light in the UV portion of the spectrum, which is about 3% of the available solar energy. [3-5] This limitation has motivated attempts to modify the absorption edge of titania so that it can absorb visible light.One strategy is to substitute a portion of the titanium and/or the oxygen with other atoms. There are numerous reports on visible light absorption of titania by doping and co-doping of Cr, V, Mo, Sb, Fe, N, S, C, and F. [6-34] Another strategy is to add an adsorbed molecular species that absorb visible light and donate an electron or hole to the titania, such as organic dyes [33, 35, 36] and Ce3+/Ce4+. [37, 38]The strategy in the present work takes the approach of depositing a pure titania thin film on a visible light absorbing substrate BiFeO3 to induce visible light activity of the heterostructure. BiFeO3 is a semiconductor with a band gap of about 2.5 eV [39-41] and is photocatalytically active in visible light. [42, 43] It is also ferroelectric with spontaneous polarization along pseudo-cubic <111> directions of 6.1 µC cm-2. [44] The spontaneous polarization gives rise to internal electric fields that drive photogenerated charge carriers, namely electrons and holes, in opposite directions to reduce their chance of recombination. [45-47] Additionally, the separation of electrons and holes leads to the spatial separation of reduction and oxidation half reactions so that the back reaction of intermediates is also suppressed. Such charge carrier separation has been reported in TiO2/BaTiO3 heterostructures with UV light illumination. [48-51] The TiO2/BiFeO3 heterostructures in this work combine both advantages of the relatively narrow band gap and the internal fields in BiFeO3 to enhance the overall photocatalytic activity."

Jan 1, 2014

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By William Petrul

Image analysis studies were performed on mill products from laboratory flotation tests of the Zn-Pb ore from the Faro deposit in Yukon, Canada, to determine mineral liberations at specific grinds and to predict recoveries at optimum flotation conditions. The minimum and optimum grinds for liberating sphalerite and galena were predicted from size analysis data for the minerals in large ore pieces, and determined by image analysis studies of the mill products. The determined optimum grinds are about 2 Tyler mesh sizes larger than predicted because sane of the fine grained sphalerite and galena occurs in interstices between coarser grained pyrite and is liberated when the pyrite grains are broken apart. Materials balance calculations were performed on the analyzed values for the liberated and unliberated sphalerite and galenaa to determine their distributions in the mill products. The laboratory flotation tests recovered 74% of the sphalerite and 83% of the galena in Zn and Pb concentrates respectively. The mineral evaluation study indicates that the optimum recovery for sphalerite and galena are 85 and 83% respectively. The company is currently recovering 80% &apos;of the sphalerite and 82% of the galena.

Jan 1, 1989