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By R. M. Cunningham

Asarco operates one of the largest individual copper electrolytic refineries in the world at Amarillo, Texas. The feed for this refinery is a mixture of anodes produced at Asarco smelters and copper purchased t?om a number of primary and secondary sources. The variation in feed makes it imperative that the refinery practices state-of-the-art quality control to minimize the effects'of unwanted impurities in the electrolytic refining process. In late 1993, a plant designed to sigru6cantly reduce the antimony and bismuth levels in the electrolyte was commissioned. The purification plant uses ion exchange technology in conjunction with a novel strippiing system developed by Zeneca Specialties (U.K.). The strippiing system permits the recycling of the eluant and thus avoids the extremely high costs of stripping with conventional reagents. In addition, the environmental impact of treating the eluant for recovery of antimony and bismuth is minimized. This paper outlines the development of the technology and, in particular, describes the operational practices and improvements at Amarillo since the commissioning of the plant.

Jan 1, 1997

By Abbas H. Mirza

Arsenic and selenium are found in low quantities together with other metals in several nonferrous metallurgical process streams such as scrubber blowdown solution, acid plant wastewater, gas cleaning plant water, etc. Normally, the other metals in these streams are present as cations and can be precipitated by conventional lime treatment and sulfide polishing. However, arsenic and selenium are invariably present as anions, AsO33-and AsO43 in the case of arsenic and SeO32 and SeO42 for selenium. Conventional lime treatment removes most of the arsenic, but it does not remove selenium. The present paper reviews the processes and technologies developed to date on the removal of arsenic and selenium from metallurgical process streams.

Jan 1, 1996

By Linda C. White

The use of red mud, a waste product of the ?Bayer? process for bauxite refining, was investigated for its arsenic removal effectiveness from aqueous solutions under various conditions. Red mud efficiently removed As(III) between a pH range of 7.6 and 9; and As(V) in the pH range between 5.5 and 6. Pre-washing of the red mud with salt water considerably improved its arsenic adsorption capabilities. With appropriate red mud dosage, the residual arsenic in solution was decreased below the regulated acceptable arsenic limit (0.1 mg/L) from aqueous industrial wastes. The arsenic adsorption followed first-order rate kinetics and fitted the Langmuir isotherm model. Results suggest that red mud is potentially a useful adsorbent for removal of arsenic from contaminated water or industrial waste solutions.

Jan 1, 2003

By Luiz A. Teixeira

This paper reports the results of kinetic studies involving the precipitation of arsenic from aqueous solutions as FeAs041 Fe(OH)3' using FeS04 as source of Fe ions, and Air or H202 as oxidizing agents. Both systems lead to an efficient removal of arsenic. The differences in oxidants performances are in the precipitation reaction rate -much faster using hydrogen peroxide. Mechanisms of reactions were suggested based on the following main steps:

Jan 1, 1996

By Gunther Klamp

Disposal of arsenic compounds from washing acid in metallurgical plants is becoming a severe problem when using lime neutralization. A further problem is the disposal of relatively large quantities of gypsum which is produced during this neutralization step and which Is also conta-minated with other toxic metal compounds. The Sachtleben-Lurgi process removes arsenic and other metals from washing acid in the form of insoluble sulphides. The purified acid contains less than 0.5 ppm of arsenic and can be used for standard sulphuric acid applications. The process Is demonstrated commercially at Sachtleben's acid plant since more than five years.

Jan 1, 1992

By Christina V. White

An experimental study was undertaken to investigate the feasibility of utilizing vapor transport for the treatment of heavy metal contaminated smelter soils. The focus of this project was to develop process chemistries that would make incineration a viable process for the treatment these soils. The experimentation concentrated on the elimination of arsenic, cadmium, and lead, and was performed in a laboramry scale rotary kiln setup. Three soil samples from non¬ferrous smelter sites, which contained various concentrations of contaminants, were utilized in the experimentation. Three chemistries were investigated for the volatilization of the heavy metals: Chloridizing volatilization, ferric chloride vapor complex formation, and the use of oxygen potential control. The samples were analyzed for residual heavy metals so that the extractions could be determined. However, the ultimate test was the leachability of the residual arsenic, cadmium, and lead, as determined by the TCLP test. The results firmly establish that incineration is a feasible process for the treatment of metal contaminated soils. It was found that no one process chemistry is suitable for all different soil samples. A two-step process consisting of a reducing step followed by a hydro-chlorination step was required to make Soil Sample-B pass the TCLP tests for all three heavy metals. Soil Sample-A passed the TCLP tests for arsenic, cadmium, and lead using a hydro-chlorination process at a minimum temperature of 700°C. In addition to passing the TCLP mm for Soil Sample-A and Soil Sample-B, 70 to 80 percent removal of the impurities was accomplished. This demonstrates that the leachability of the impurities was decreased primarily due to the removal of a large fraction of the contaminants, Soil Sample-C possessed very high levels of cadmium and lead and only moderate extractions of the impurities were generated from this soil. The arsenic TCLP test was passed at 500'C using a process gas containing ferric chloride and at temperatures of 700°C and above using chlorination of hydro-chlorination.

Jan 1, 1996

By Baozhong Zhao

The direct smelting of copper concentrates to copper metal in a single furnace offers environmental and energy advantages over conventional two-stage copper smelting processes. However, the direct copper making results in unacceptably high level impurities (As, Sb and Bi) in the anode copper. Experimental studies have shown that it is possible to remove these impurities from molten copper by injection of sulfur-hexafluoride. This paper discusses the experimental findings on the influence of various factors on the rate of removal of impurities, such as the impurity inter-effects, initial oxygen content in the metal and injection rate of SF6.

Jan 1, 1995

By Mitsuru Tanahashi

In order to develop an effective process for the production of a solar-grade silicon (SOG-Si) from metallurgical-grade one (MG-Si), the oxidation removal of boron from molten MG-Si was investigated at 1773 K by the following two CaO-saturated CaO-CaF2 flux treatment processes. I) Boron removal by flux addition onto the molten MG-Si followed by oxygen gas injection into the melt (Two-stage connecting process). II) II) Boron removal by simultaneous injection of flux powders and oxygen gas into the molten MG-Si (Simultaneous injection process). These processes can establish the special condition of both high basicity of the flux and the high oxygen partial pressure at the boron removal reaction sites. Through these processes, especially by the simultaneous injection process using a flux powder injection equipment, the boron content in MG-Si can be efficiently reduced. The obtained results clarified that both processes should be conducted for a time period as short as possible by using as much flux as possible. By repeating the simultaneous injection process for 60 s three times under the optimum operating conditions determined in the present study, the boron content in MG-Si can be reduced from 14 to 4.7 mass ppm.

Jan 1, 2003

By Mitsuru Tanahashi

In order to develop an effective process for the production of from metallurgical-grade one (MG-Si), the oxidation removal of boron from molten MG-Si was investigated at a solar-grade silicon (SOG-Si) 1773K by the following two CaO-saturated CaO-CaF2 flux treatment processes. I) Boron removal by flux addition onto the molten M6-8 followed by oxygen gas injection into the melt (Two-stage connecting process). II) Boron removal by simultaneous injection of flux powders and oxygen gas into the molten MG-Si (Simultaneous injection process). These processes can establish the special condition of both high basicity of the flux and the high oxygen partial pressure at the boron removal reaction sites. Through these processes, especially by the simultaneous injection Process using a flux powder injection equipment, the boron content in MG-Si can be efficiently reduced. The obtained results clarified that both processes should be conducted for a time period as short as possible by using as much flux as possible. By repeating the simultaneous injection process for 60 s three times under the optimum operating conditions determined in the present study, the boron content in MG-Si can be reduced from 14 to 4.7 mass ppm.

Jan 1, 2003

By Luciano E. Ramírez, Jesús L. Valenzuela, José R. Parga

"An innovative process for removing copper cyanide complexes including silver and zinc from cyanidation circuits has been developed. The technology was based on the inducing the nucleated precipitation of copper and silver in a tube serpentine reactor, using sodium sulfide as the precipitate and sulfuric acid as pH control. The results showed that pH had a great effect on copper cyanide removal efficiency and the optimum pH was about 3 to 3.5. At this pH value copper cyanide removal efficiency could be achieved above 97 and 99 % ,when influent copper concentration ions were 650 and 900 ppm respectively. In this process (sulphidizaton-acidification-recycle-thickening), the cyanide associated with the copper cyanide complexes is released as HCN gas under weakly acidic conditions, allowing it to be recycled back to the cyanidation process as free cyanide. This system was successfully commercial applied at Minera William in Mexico.IntroductionThe recovery of gold and silver from minerals and concentrates with cyanide is an important hydrometallurgical process, which has been studied for more than 124 years. Patented by MacArthur in 1888 [1], the process relies on the fact that gold dissolves in aerated cyanide solutions to produce the gold cyanide complex. The stoichiometry by wich this reaction occurs is known as the Elsner equation as shown here. Silver is accomplished in the same fashion."

Jan 1, 2012

By A. V. Tarasov, S. D. Klushin

493 The most common method for minimizing the copper content of residual slag in the process of autogenous smelting of sulfide raw materials is treatment of molten slag in an electric furnace, with optional addition of solid reducing agents, such as coke, and/or sulfiding agents such as pyrite. A drawback of this technique is the fact that the final slag produced still contains 0.5% or more Cu. We have tested a method for treating molten slag obtained as a result of autogenous smelting by a gaseous mixture of sulfur dioxide and methane at a ratio of. SC:SO2 = 0.75 :1.0 in the presence of oxygen. Interaction reaction within the SO2-O2-CRi system proceeded at a high rate at 1373 to 1573 K to form reducing and sulfiding agents: H2S, S, COS, CO, CO2, H2, H2O. The gas mixture requirement was about 100 to 150 Nm3 per 1 tonne of slag. A decrease in the ferric iron concentration (Fe3+) from 10-15% down to 2-3% resulted in lower solubility of copper in slag, and agitation of the melt with gas stream accelerated. the separation of the sulfide phase and slag. Removal of copper from slag was performed in a pilot unit within the second V anyukov furnace zone where slag arrived with a copper content of 0.8-1.3%. The temperature of molten slag was maintained within 1523 to 1573 K. The copper content of the final slag was at a level of0.12 to 0.14%. The matte sent to converting was a mixture of bottom matte from the smelting zone and the slag treatment zone. It had a copper content of about 50 to 55%. Process gases from both furnace zones were combined and sent to the acid plant for sulfur recovery. This process was offered for commercial use at two copper smelters in Russia and CIS.

Jan 1, 2000

By Donna L. Bodine

The ability of oxidized Upper Freeport bituminous coal to adsorb Cu2+, Cd2+ and Mn(VII) from very dilute aqueous solutions has been studied. Low-rank coal is known to adsorb heavy metal ions from dilute, aqueous solutions, probably by ion exchange and/or chelation by acidic functional groups on the coal surface. However, it would be advantageous to use higher rank coals for water treatment. Coal samples were oxidized thermally or by 30% H202 to increase the surface concentration of phenolic and carboxylic groups, then portions were shaken with Cu2+ and Cd2+ solutions. Acidic KMnO4 was also used to oxidize coal, with concurrent sorption of the resulting Mn(IV) and Mn(ll). The effect of oxidation treatment, metal ion concentration, and solution pH on metal uptake kinetics was investigated. Potential applications for treating effluents, especially those containing oxidizing ions, are discussed, along with possible flowsheet options.

Jan 1, 1995

By Jerome P. Downey

In the thermal treatment of electric arc furnace (EAF) dusts, zinc is reduced, volatilized, and ultimately recovered either as liquid metal in a splash condenser or as solid zinc oxide in bag filters. During the process, the duet's chlorine and fluorine content also enters the gas phase and condenses as dross in the splash condenser or as salts which contaminate the zinc oxide product. Pretreatment of EAF dust by pyrohydrolysis appeared to offer a means of minimizing the duet's halogen content. The primary research objectives were to experimentally verify the technical viability of pyrohydrolysis and delineate the process parameters requisite for efficient halogen removal. To this end, representative EAF duet samples were secured and characterized by x-ray diffraction, scanning electron microscopy, and Mössbauer analyses. Specific- experimentation focused on the response of halogen extraction to variations in temperature, retention time, water vapor partial pressure, and various additives. The experimental results proved that 97 to 99 percent chlorine extraction and 80 to 85 percent fluorine extraction are consistently achieved when EAF dusts are blended with silica and roasted at temperatures of 850°C or greater in a furnace atmosphere of 75% steam (diluted by air). A statistical analysis further established that more than- a single optimal point exists, thus affording flexibility in parameter selection (e.g., by increasing temperature, the necessary retention time and additive concentrations are decreased). The findings substantiate the feasibility of pyrohydrolysis roasting in reducing the chlorine and fluorine in the EAF dust to a level that will obviate industrial concerns about halogen contamination. The end-product of the pyrohydrolysis procedure is a de-halogenated, self-fluxing calcine which can be directly charged to a plasma or flame reactor. The paper includes design parameters and flow diagrams illustrating the pyrohydrolysis process integrated with the plasma and flame reactor technologies.

Jan 1, 1992

The generation of acid mine water is? due to the oxidation and weathering of sulfide bearing tailings and overburdens. Ferrite precipitation prooess has been applied to treat acid mine water. The conventional ferrite preC1pitatlon requires air oxidation at high temperature, or long aging time or addition of magnetite powder ,as promoter. In this investigation, a modified ferrite, precipitation process is developed by which magnetic ferrite can be produced at an ambient temperature. Acid mine waters from Berkeley Pit (Montana, U. S. A.) and from Noranda Tailings (Quebec, Canada) were used. The co precipitation of heavy metals from these two acid mine waters is studied as a function of FeIM molar ratio, oxidation time and settling rate under applied magnetic field. The investigation indicates that the modified ferrite co precipitation can remove substantially all of the, dissolved metal ions from acid mine water. The ferrite product obtained after precipitation' is characterized by XRD, SEM, BET and saturation magnetization. The results show that spinel ferrite, precipitation can be achieved at room temperature and the saturation magnetization of ferrite product from,acid mine water is comparable to that of pure ferrites.

Jan 1, 1995

By Yang Jian-guang, Deng Zi-xiang, Zhang Xu-liang, Li Jun-yuan

"Hyperaccumulator biomass harvested after heavy-metal phytoremediation must be considered as hazardous waste that should be contained or treated appropriately before disposal or reuse. As a potential method to detoxify the biomass and to convert this material to a suitable bio-energy resource, the hydrothermal upgrading process was applied to remove heavy metals and upgrading crude bio-oil from Pteris vittata stems and leaves harvest. Parameters such as material granularity, temperature, Liquid/Solid (L/S, ml/g), pressure, duration and catalysts were examined for their effect on the removal efficiency of heavy metals and upgrading efficiency of crude bio-oil. Maximum heavy metal removal efficiency of>99% and crude bio-oil upgrading efficiency of 83% were attained with an 200 mesh (75 µm) granularity, LIS 40:1and23 MPa at 380°C in the presence ofO.l mol L-1 K2C03 for 30 min. GC-MS analysis results show that the resulting bio-oil mainly consists of benzene 11 %, ketone 42%, alcohols 14%, alkene 15% and ester 11 %, etc., and the relative molecular weight distribution lies in 94-282, carbon number distribution lies in 6-18, calorific value is 32MJkg-1.IntroductionPhytoremediation of soil or water with hyperaccumulator has been extensively explored in recent years [1-4]. Living plants can clean up soils or waterways. This approach exploits the ability of various plant species to thrive in high metal environments where large amounts of toxic elements are accumulated, such as heavy metals, and is particularly appropriate when slow remediation of relatively low metal concentrations is acceptable. Advantages compared with existing remediation methods include the minimal site destruction and destabilization, low environmental impact, and favourable aesthetics; advantages compared with biosorption include continuous in situ regeneration of the biomass, and the ability of living plant cells to supplement passive sorption of metals with metabolic mechanisms of metal uptake and detoxification [5-8]."

Jan 1, 2014

By C. Koopman

During the production of phosphoric acid from phosphate ore and sulfuric acid, large amounts of calcium sulfate are formed, in which impurities from the feedstock are incorporated. To use the calcium sulfate in, for example, the building industry, a lower concentration of impurities is desired. Mercury, copper, lead, and cadmium were extracted from clear industrial recrystallization acid (0.8-3.9 mol/kg H3PO4, 0.2-0:5 mol/kg H2SO4) by supported solvent extraction with the extracting agent Cyanex 302 in kerosene in a transverse flow hollow fiber module. The permeability for the mercury ion was 1.4.10-6 m/s, whereas that for the copper ion was calculated to be 1.5.10 m/s. Cadmium, lead, and copper were extracted during the recrystallization of calcium sulfate hemihydrate to dihydrate, an existing step within the ,phosphoric acid production process, by solvent extraction with the same extracting agent. The concentrations of cadmium and zinc in the newly formed calcium sulfate were proven to be decreased. Unfortunately, concentrations of mercury and lead were too low for analysis.

Jan 1, 1999

By Carl C. Nesbitt

A study was conducted to examine the treatment of metal-bearing effluents by precipitating the metals as sulfides and simultaneously collecting the particles by flotation. The precipitant was hydrogen sulfide gas which was introduced into a bench-scale column cell with air. The study included experiments of various flotation reagents and column configurations in treating solutions containing dissolved copper, lead, mercury, iron, zinc and cadmium. An acidic laboratory waste from a local copper operation was used to test the column with a solution containing several metals and arsenic. Precipitates were observed to form at the gas/liquid interface when the gas mixtures were rich in H2S. Copper, mercury, lead, and cadmium were precipitated from solution as sulfides to concentrations near detection limits. The flotation of these precipitates was enhanced with small amounts of S-7151 promoter from American Cyanamide Company and Dowfroth 1263 mixed with the feed. The recovery of the precipitates in this manner produced a smaller volume slurry which was easier to dewatering than a slurry produced by conventional precipitation techniques. The low pH and high oxidation-reduction potential in the cell from H2S addition was not conducive to form precipitates of iron, zinc or arsenic. However, these ions were precipitated as sulfides by raising the pH of the column discharge.

Jan 1, 1994

By Hal dun Kurama

In thus-study, Bigadic upper zone zeolitic tuff, which contains about 87% clinoptilolite was used as an ion exchanger for removal of Pb++, Cu++, Cd++ and Hg++ ions from wastewater. Bench scale experiments with two different glass columns, were carried out continuously under the closed/ open circuit conditions. Before ion exchange tests, zeolite samples were treated with NaCI (6ml/ min. and 42BV). The effects of particle size, bed volume, pH and flow rate on the ion exchange capacity were determined. Under the best operation conditions, the effect of initial influent solution concentration on ion exchange selectivity was tested. As a-result, it was found that the Bigadiç clinoptilolite had the following ion exchange capacities;

Jan 1, 1995

By Liyuan Chai

In this study, spent grain was used as an adsorbent for the removal of Hg(II) from aqueous solutions, the process parameters such as contact time, solution pH, adsorbent dose, and initial Hg(II) concentration were studied in batch experiments. The initial adsorption process was fast, 91.08% of adsorption occurred within 5 min and equilibrium was reached at around 30min. Adsorption process was found to follow pseudo-second-order kinetics. The equilibrium data were better fitted to Langmuir isotherm than Freundlich isotherm with the maximum adsorption capacity 41.36 mg/g. The structure and component of spent grain before and after adsorption of Hg(II) were investigated using scanning electron microscope(SEM) and energy dispersive X-ray analysis(EDAX), these analysis also confirmed the adsorption of Hg(II) onto spent grain. The results indicated that spent grain had potential as a new inexpensive adsorbent for Hg(II) removal from aqueous solutions.

Jan 1, 2009

By T. Kamata, S. Takemoto, H. Takeuchi, M. Takayanagi, Y. Akahori, I. Jimbo

"A cooperative research work on the silver recycling process is underway between Matsuda Sangyo Co., Ltd. and Tokai University in Japan. Silver wastes treated here are mainly from photograph industries where the concentration of minor element is steadily increasing in the recent years. The waste materials are concentrated and the impurities are removed by evaporation and slagging. In this paper, the industrial practice of wastes treatment is introduced and the result of the laboratory studies on the removal of antimony and tin from the binary and ternary alloys will be discussed. Characteristics in the behavior of antimony and tin during the process are also discussed with the observation of practical operation.1. IntroductionPrecious metals such as gold and silver primarily come from mining practice and the byproduct in copper smelting. However, the recycled amount of these precious metals have been increased 1 along with the environmental restriction and the widely accepted idea of saving resources on the earth in the recent years.· Though the recycle process of precious metals are comparatively simple from other metals refining, the process has been getting more complicated as wastes treatment has to deal with more impurity elements which are intentionally added to the products. Among these additives, antimony is used in the film materials in the photography industries to suppress its inflammability. Tin is another concern ,that is also coming from photography wastes; These minor elements have become problematic during the recycle.The removal of these minor elements has been in operation at Matsuda through a traditional oxidation refinement process using a reverberatory furnace. However, the complexity of the charge makes the recycle process more tedious and troublesome. In order to investigate the minor element behavior in the complicated materials system during the silver recycling processes, a cooperative research work is undertaken between Matsuda Sangyo Co., Ltd. and Takai University in Japan. Silver wastes treated here are mainly discharged from photograph industries where the minor element contents such as antimony, tin and bismuth in those wastes are steadily increasing in the recent years. The liquid wastes containing silver are concentrated and then treated pyrometallurgically with solid wastes from other sources, where the impurities are removed ·by evaporation and slagging. The purpose of this study is to investigate detailed behavior of impurity elements in the silver. containing systems."

Jan 1, 2000