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By Alejandro R. Alonso, Lizet Alvarado, Gretchen T. Lapidus

"Cobalt and lithium recovery from spent Li-ion secondary batteries has been increasingly studied in recent years due to the high value of both metals and the low proven reserves for lithium. The standard method employed until now has been the deactivation and crushing of the batteries, followed by leaching of the L1C0O2 spinel from the battery cathode using acid solutions, such as 1.5 to 2.0 M HC1 or H2SO4, in a temperature range from 120°C to 250°C. Once leached, the cobalt is separated by electrodeposition and the lithium by precipitation, using large amounts of carbonate to bring the solution to alkaline pH values. In the present work, citric-thiosulfate solutions are used for the spinel leach at room temperature, favoring a reductive environment at room temperature, which stabilizes the cobalt(II) as cobalt citrate and lithium(I) at pH 5, and recovers approximately 99% of both metals.IntroductionThe Li-ion batteries industry has become an important economic sector in recent years. This type of battery is the most promising system for energy storage, because of its high efficiency in charge-discharge cycles, and its adaptability to many configurations. The demand will probably increase because of the need for mobile energy sources in many types of devices ranging from cell phones, tablets, and laptops to medical, navigation and sophisticated communication equipment and even in automobiles.One major problem related to the use of these batteries is the method employed for recycling the components, mostly cobalt and lithium. Currently, there are two processes employed on an industrial scale: the Sony/Sumimoto process, used since 1990 [1] and the Toxco Process [2]. In the first case, incineration is used to open the batteries and at same time volatilize the organic solvents. After that, the metals (copper, iron and aluminum) are physically separated. The cobalt and lithium are recovered as oxides and then thermally treated in order to recycle them for new batteries manufacture."

Jan 1, 2012

By Roger Agnew

Sulphide ores mined by Inco Limited in the Sudbury District contain small quantities of cobalt. During beneficiation, cobalt distribution to various streams is similar to nickel. After smelting, nickel is selectively extracted by carbonyl refining and the cobalt remains in the carbonylation residue. This residue is processed in a specialized hydrometallurgical plant to produce precious metal residues, copper cathodes, and a nickel- cobalt carbonate intermediate product. The nickel-cobalt is shipped to Port Colborne where the cobalt is separated as cobaltic hydroxide and refined to metallic cobalt. This paper deals specifically with the recently constructed Electro Cobalt Refinery. The cobaltic hydroxide is dissolved and residual zinc, copper and nickel are removed by ion exchange and organics by a carbon column. The purified cobalt solution is fed to the electrowinning circuit where cobalt rounds are produced on stainless steel mandrels. In the design and construction of the refinery, special attention was directed to materials of construction both for the process equipment and the physical plant, operating control and flexibility, and the quality of the working environment. The end result is an efficient and clean operation which yields a product of excellent quality.

Jan 1, 1988

By R. Hammen

Processes are needed to rapidly and cost-effectively produce highly pure lithium salts for the rechargeable battery sector. Lithium purification is a chemical engineering challenge, due to the low concentration of lithium compared to sodium, potassium, magnesium, calcium, and transition metal ions commonly occurring in lithium brine resources. We describe a Solid Phase Extraction (SPE) process that rejects sodium and potassium, while binding lithium and other higher valent ions. Lithium is then harvested by selective displacement from the SPE column. The rapid equilibration kinetics of SPE composites enables these ion separations to occur in a small SPE column and in one column stage. The chemical parameters of the process are described.

By Santo Ranieri

We will briefly review the nickel market in 2003 and look forward to the supply demand balance for the next few years focusing in on the key factors influencing future price dynamics. On the supply side we will examine slated brownfield and greenfield expansions including the Norilsk factor and the small to mid-range 'supply creep'. We will also review the cost side of the industry and what to expect going forward. On the demand side, we will discuss the stainless steel and non-stainless demand, the China factor and the stainless steel scrap supply cycle. We will conclude by pinpinting where the market is on the current price cycle, and where we believe the mid-term direction is headed.

Jan 1, 2004

By M. C. Ruiz

This work outlines the results of leaching studies on a copper concentrate containing chalcocite (Cu2S) and digenite (Cu9S5) with an acid saline solution of cupric chloride oxygenated at ambient pressure. The variables studied included the stirring speed, concentration of cupric ions, concentration of HCI, concentration of chloride ions, oxygen flow rate, temperature and time. The leaching system was found to be very effective for the dissolution of the concentrate. Over 95% of the copper was dissolved in 30 minutes with negligible dissolution of iron. The dissolution of copper increased with the stirring speed up to about 400 rpm and depended little on the total chloride concentration. The oxygen flow rate affected the dissolution of copper only below 0.1 1/min. The concentration of HC1 did not influence the dissolution providing its was sufficient to avoid the precipitation of copper oxychloride. The study of the effect of the temperature showed a maximum in copper dissolution around 90 "C

Jan 1, 1997

By Hideaki Tokuyama

Recovery of Ni from acidic wastewater of metal surface treatment has been investigated for reuse of the metal and water. Ion exchange equilibria between Ni ion and a strong acid cation resin, DIAION SKIB, and effective diffusivity in resin particle have been studied and they related to the concentration of HCI. The amount of adsorbed Ni for unit quantity of resin decreases with the increase in HCI concentration. This trend is remarkable for acid concentration above 0.1 kmol/m3,. The exchanging ratio of Ni2+ to H+ in resin particle is I/2 and the values of equilibrium coefficient K and maximum exchange capacity Q are I.62 and 3.16 keq/m3 -dry resin, respectively. Effective diffusivity D. determined from the observed breakthrough curve increases with increasing concentration of DC!. A prototype of moving bed has been developed and applied for the recovery of Ni from model solutions of wastewater prepared by mixing HCl and NiCl2. This apparatus allows us to control the resin flow rate by changing the cross sectional area of hole I the Teflon plate installed at the bottom of resin bed. Characteristics of Ni recovery have been clarified under various liquid flow rates. In any case for Q1, Ni ion has been effectively recovered on SKIB resin and the removed fraction was more than 99.5 %. Higher loading ratio of ion is attained at larger liquid flow rate.

Jan 1, 2003

By M. J. Collins, L. C. Trytten, K. R. Buban, I. M. Masters

Both pressure leaching of zinc concentrate, in an autoclave, and atmospheric leaching, in stirred tanks, have been employed in the expansion of zinc production at plants employing roast-leach-electrowin technology. These direct leaching methods result in the conversion of the sulphur in the feed to the elemental form, rather than to sulphur dioxide, decoupling zinc production from acid production. Atmospheric and pressure leaching methods are also readily implemented over a wide range of production rates. In choosing the best technology for expansion, capital and operating costs, zinc recovery, byproduct quality and the compatibility of recycle streams with the existing refinery must be compared. Leach testwork with several zinc concentrates using both methods has been performed by Dynatec. Recent results are presented, along with a discussion of their implications for process selection.

Jan 1, 2000

By Berndt Moeller

Mercury-cell chlor-alkali production plants generate mercury contaminated wastewater streams from which mercury must be precipitated and filtered, resulting in a sludge containing 2% mercury (designated KI06) that cannot be landfilled in the United States without treatment. REMERC is a chemical treatment process used to recover 99% of the mercury from wastewater sludge generated at these plants. The process uses leaching to oxidize mercury compounds to mercuric chloride, washing and filtration to separate mercuric chloride from the treated sludge, and cementation to reduce the mercuric chloride to metallic mercury. Mercury not recovered in cementation is recycled to the wastewater process for precipitation and filtration. Treated sludge contains less than 260 ppm total mercury and 0.2 ppm TCLP, meeting the USEPA low mercury subcategory specifications that allow landfill disposal. REMERC uses readily available chemicals, is straightforward to control and inexpensive to operate, has no mercury emissions to air, and recovers metallic mercury. REMERC enabled significant cost savings including lower solids disposal costs, recovery and reuse of metallic mercury in the chlor-alkali process, and ability to treat non-wastewater sludge. No new EPA permits were required. REMERC was shown to be a viable process for recovery of metallic mercury from K106 designated sludge.

Jan 1, 2003

By Cesimiro Fabian

The crystallite size of copper electrodeposits was determined by X-Ray powder diffraction analysis using a General Area Detector Diffraction Solution (GADDS) diffractometer. Crystallite size was calculated for copper thin films which were deposited on a 316 stainless steel rotating cylinder electrode (RCE) in the presence and absence of additive ?A?. The crystallite size was calculated from a corrected full width at half maximum (FWHM) of the [110] peak profile using the Scherrer equation. The test of significant difference on crystallite size was derived using Kruskal-Wallis method. It was found that in the absence of the additive the median crystallite size was 426, which decreased to 364 in the presence of the additive. As the additive degraded, the crystallite size increased to a size similar to that observed in the absence of additive.

Jan 1, 2003

By Qingyu Deng, Shiwei Ma, Wang Hua, Guibao Qiu

"The flow properties of the blast furnace slag bearing high TiO2 at high temperature like the viscocity may change a lot due to the formation of the carbonitride inside, causing serious problems on the separation between the metal and the slag. Therefore, the critical condition of the formation of Ti(C,N) in blast furnace is vital importance for the ironmaking process with iron ore bearing titania. In this study, the formation of Ti(C,N) in blast furnace and the influences of various factors on the Ti(C,N) formation are investigated by FactSage. It is found that the mass of Ti(C,N) would reach the maximum at 1480 oC, and the product is mainly TiN below 1620 oC, while it is mainly TiC above 1620oC. The order of the factors by the importance from strong to weak was: temperature, the content of TiO2 in slag, basicity of slag, the content of MgO and Al2O3.IntroductionThe titanium dioxide (TiO2) in iron ore bearing titania will be partly reduced by carbon to titanium carbonitride (Ti(C,N)) in blast furnace, causing serious problems on the separation between the metal and the slag because of the change of flow property. Therefore, the critical condition of the formation of Ti(C,N) in blast furnace is vital importance for the ironmaking process, especially for the smelting of iron ore bearing titania. Extensive experimental data in regard to the formation of Ti(C,N) has been reported in numerous papers[1-6]. However, only some discrete data can be obtained by experiment, and it is difficult to detect the mass of Ti(C,N) in slag. In addition, the experiment is difficult to be proceeded when the temperature is above 1600oC. Therefore, it is very difficult to make clear the critical condition of the formation of Ti(C,N) by experiment."

Jan 1, 2012

By Yong-ming Chen, Chao-bo Tang, Yun Li, Long-gang Ye, Sheng-hai Yang, Hao-tian Xue

In order to achieve high recovery of Cu and Co during cobalt-bearing copper sulphide ore smelting process, reducing agent (coke) and sulphidizing agent (pyrite) were added into molten smelter slag for reducing-sulphidizing smelting to product Cu-Co matte. Effects of reductive atmosphere, pyrite dosage, smelting temperature and smelting duration on Cu, Co, Fe distribution behaviours were investigated. The results show that the distributions of Cu and Co are mainly enriched in Cu-Co matte, and the distribution ratio, LCu and LCo, improve with increasing of coke amount or pyrite addition, whereas above 6 wt.% coke or 20 wt.% pyrite, Cu and Co tend to transfer from matte to cleaned slag. A properly high temperature(1300) and smelting duration(3h) are beneficial to the enhancement of the distribution ratio of valuable metals, and under the given set of conditions, LCu > LCo generally. However, an undesired high Fe contents in matte limit further increase of LCu and LCo.

Jan 1, 2015

By Kurt Westerlund

Three. years operating experience of the FLUXFLOW waste heat boiler (WHB) 20.000 nm /h at Boliden Ronnskar Sweden on a TBRC smelting palena (PbS). Operating experience from the Kivset flash WHB 11.900 nm /h at Samim, Porto Vesme, Sardinia, Italy. Conceptual features of the 93.600 nm3 /h FLUXFLOW (WHB) on the Isasmelt smelting in melt furnace for 180.000 t Cu/a at Mount Isa, Australia.

Jan 1, 1992

By M. Okido, H. Yamamoto, T. Sakamoto, R. Ichino, K. Kuroda

"Hydrogen absorption alloy films have been produced by molten salt electrolysis. Lanthanum-Nickel alloy film can be formed on a nickel substrate in KCl-NaCl-LaCb molten salts by electrolysis diffusion process. LaNi5 alloy was formed by mutual diffusion between La ·and Ni after La deposition on Ni substrate. Though several kinds of La-Ni compound existed in deposits, the alloy compounds on Ni substrate changed by electrolysis condition. According to the open-circuit potential measurement in molten salts after La electrodeposition, the formed compounds had a relation to the potential. In the case of the substrate electroplated a cobalt thin film on nickel, LaNi4_5Co0.5 was formed by the electrolysis in the molten salts with lanthanum ions. This ternary alloy film showed better hydrogen absorption behavior in cyclic charge/discharge test in alkaline solution.IntroductionHydrogen storage alloys have attracted attention as the active materials for batteries with the charge/discharge property at ambient temperature. The alloy of nickel and misch metal, mainly consisting of La and Ce, has been commercially 'used as a metal hydride with rechargeable property. In recent years, researches have been developed many kind of new alloys with better hydrogen absorption properties. The hydrogen absorbing alloy ingots are commonly produced by melting method of both metals in furnace, otherwise, prepared by mechanical grinding and metallurgical sintering technique with metal powders. The film is also made by vapor-phase techniques such as sputtering method, ion plating method, etc. ·We have proposed a new method to produce hydrogen absorbing alloy films by molten salts electrolysis technique [1-3]. The hydrogen absorbing film, LaNi5, Mg2Ni and CaNi5, were obtained in this process through controlling the electrolytic condition. The active metals, La, Mg and Ca, are electrodeposited on Ni substrate, diffuse into the substrate and form various kinds of intermetallic compounds. This technique provides a direct process using metal chlorides as resources to produce functional films without using active metals such as La, Ca and Mg."

Jan 1, 2000

By Ralph P. Hackl

Bacterial leaching of the Doe Run Company?s cobalt/nickel-containing copper concentrate at low pH (pH 1.0-1.2) and high redox potential (>750 mV vs. SHE) enabled the cobalt and nickel to be preferentially dissolved over copper and iron due to the rapid passivation of the chalcopyrite component. Selective leaching of the cobalt and nickel was achieved with a mesophilic culture comprised mainly of Leptospirillum-like bacteria and Acidithiobacillus thiooxidans. This finding led to the conception of a novel hydrometallurgical process for passivating chalcopyrite and recovering the cobalt and nickel. The bacterial leaching process was tested extensively at the bench and pilot plant scales during 1997-1998. A pilot plant containing four leaching stages processed 30-40 kg/day of chalcopyrite concentrate continuously for 87 days. The cobalt extraction ranged from 75% to 86% during 6- and 8-day retention times respectively, whereas the copper extraction was limited to about 9%

Jan 1, 2003

By Tatsuki Uzawa, Takashi Nagai

The consumption of Nd and Dy is increasing dramatically because of an exceptionally high demand for Nd-Fe-B-(Dy) magnets and a significant amount of the magnets are wasted. It is important to develop a recycle process the elements from the wasted magnets. In this study, Nd and Dy were extracted from the magnets by silver at high temperature. Nd can be extracted more than 70 % by silver. However, Dy is extracted only 25 % in the same experimental condition.

Jan 1, 2014

By Dong Hoon Han

The simultaneous sulfation by sulhr dioxide and oxygen of CaO and MgO in calcined CMA (calcium magnesium acetate) were investigated. he experiments were carried out in the temperature range from 700 to 830 "C and at the SO2 concentrations of 0.3 to 1 mol %. The oxygen concentration was kept at 5 %. Each sample was calcined completely before the temperature was lowered to the sulfation temperature. According to the ranges of partial pressure of sulhr dioxide and temperature, there exist three regions for the sulfation reaction: region I in which neither oxide is sulfated, region I1 in which only CaO is sulfated, and region 111 in which both oxides are sulfated. It was shown that the MgO in calcined CMA is sulfated at a rate comparable to that of CaO by forming a mixed sulfate phase. Thus, unlike MgO contained in other desulhrization materials, the MgO content in calcined CMA can be fully utilized for flue gas desulhrization.

Jan 1, 1999

By Tateo Usui

In the course of carbonization of coal under a rising temperature condition, volatile matter (V.M.) is released. The kind and amount of V.M. released depend on the kind of coal. Components of V.M. are tar, hydrocarbons (CH4, C2H4, C2H6, C3H8), CO, CO2 and H2, which are released in this order as a function of carbonization temperature. When the carbonization of coal under a rising temperature condition is interrupted at a certain temperature, TC, max, semi-coal-char with residual V.M. is obtained. If some optimum interruption-temperature is chosen, small but most suitable amount of V.M., namely H2, is retained. When the semi-coal-char thus obtained is heated again under the same rising temperature conditions but up to more than TC, max (1), the residual V.M. is released from just around TC, max (1). We propose novel iron ore agglomerate bearing such semi-coal-char with some strength. While simple iron ore agglomerate bearing coal char will start the reduction reaction as solid-solid reaction at somewhat higher temperature, the proposed one will start the reduction reaction as gas-solid reaction at somewhat lower temperature but a little higher than TC, max. Samples of semi-coal-char and novel iron ore agglomerate bearing such semi-coal-char have been prepared and evaluated.

Jan 1, 2006

By R. Padilla

The reaction of chalcopyrite with gaseous sulfur has been investigated in the range 350-450 °C in order to transform this mineral into a more acid soluble copper sulfide and insoluble iron sulfide. The results of thermodynamic analysis of this system as well as the X-ray diffraction analysis of the reaction products showed that in the temperature range 350 400°C the sulfidation reaction proceeded without formation of intermediate copper-iron sulfides according to: The effects of temperature and time on the conversion of chalcopyrite were studied. Conversion of chalcopyrite reached about 80% very rapidly with increase in temperature up to about 400°C. The recovery of copper from the sulfidized samples was determined by leaching in oxygenated 1.2M H2S04, 2M NaCI solution. Copper recoveries over 90 % were obtained from samples sulfidized for 30 min at temperatures lower than 400°C.

Jan 1, 2001

By Shuqiang Guo, Dingsheng Tan, Weizhong Ding, Zunyu Hu

"The mixture of hydrochloric acid and magnesium chloride is a good lixiviant for leaching of laterite. The solution can enhance the leaching ability because of the proton activity deviated positively from ideal. Otherwise, the existence of magnesium chloride in the lixiviant affects the dissolution behavior of magnesia, which may be an advantage of the process with less hydrochloric acid consumption. An investigation of magnesia particle dissolved in strong hydrochloric acid solution has been conducted. Influences of concentration of the magnesium chloride and hydrochloric acid and temperature on magnesia dissolution were studied. The dissolution mechanism was also discussed in this paper.IntroductionThere has recently been much interest in the use of hydrochloric acid leaching processes for recovering metal from ores or secondary resources [l-41_ Compared with sulfuric acid, the use of hydrochloric acid as lixiviant offers significant advantages including faster leaching kinetics even at atmospheric conditions, higher leaching rate and greater solubility for most metal chlorides [5-61 .With the gradual decline of the nickel sulfide supply, the extraction of nickel from laterites has become increasingly attractive [7-s1. Nickel may be co=ercially recovered from laterites both by pyrometallurgical and hydrometallurgical processes. The drawbacks of pyrometallurgical processes include the requirement of high grade ores, substantial energy input and loss of cobalt bound within ores. The extraction of Ni from lower grade nickel laterites ores is suited by hydrometallurgical routes, which play an increasingly important role with depletion of higher grade deposits."

Jan 1, 2014

By Irina V. Sokol

Alloyed steel chips and swarf formed during metal processing are looked upon as additional raw material In metallurgycal production. The manuscript presents some new methods for steel waste chips and swarf cleaning. One of them Is swarf and steel chips cleaning In ethylene tetrachloride with ultrasonic assistance and following, solvent regeneration. Thermal cleaning of waste chips and swarf provides exit gas products utilization. Catalyst Influence of metal surface on the process of thermal decomposition of liquid hydrocarbons during cleaning process has been studied. It has been our experience that the efficiency of metal waste cleaning technique depends on the storage time of the swarf. Waste chips and swarf cleaning procedures presented in the manuscript have been proved economically advantageous and environmentally appropriate.

Jan 1, 1995