Lithium and cobalt extraction from LiCoO2 assisted by p(VBPDA-co-FDA) copolymers in supercritical CO2.

Supercritical CO2 (scCO2) extraction assisted by complexing copolymers is a promising process to recover valuable metals from lithium-ion batteries (LIBs). CO2, in addition to being non-toxic, abundant and non-flammable, allows an easy separation of metal-complexes from the extraction medium by depressurization, limiting the wastewater production. In this study, CO2-philic gradient copolymers bearing phosphonic diacid complexing groups (poly(vinylbenzylphosphonic diacid-co-1,1,2,2-tetrahydroperfluorodecylacrylate), p(VBPDA-co-FDA)) were synthesized for the extraction of lithium and cobalt from LiCoO2 cathode material. Notably, the copolymer was able to play the triple role of leaching agent, complexing agent and surfactant. The proof of concept for leaching, complexation and extraction was achieved, using two different extraction systems. A first extraction system used aqueous hydrogen peroxide as reducing agent while it was replaced by ethanol in the second extraction system. The scCO2 extraction conditions such as extraction time, temperature, functional copolymer concentration, and the presence of additives were optimized to improve the metals extraction from LiCoO2 cathode material, leading to an extraction efficiency of Li and Co up to ca. 75 % at 60 °C and 250 bar.

Feasibility of reduced iron species for promoting Li and Co recovery from spent LiCoO2 batteries using a mixed-culture bioleaching process.

The recovery of metals from spent LiCoO2 batteries (SLBs) is essential to avoid resource wastage and the production of hazardous waste. However, the major challenge in regard to recovering metals from SLBs using traditional bioleaching is the low Co yield. To overcome this issue, a mixed culture of Acidithiobacillus caldus and Sulfobacillus thermosulfidooxidans was designed for use in SLBs leaching in this study. With the assistance of Fe2+ as a reductant, 99% of Co and 100% of Li were leached using the above mixed-culture bioleaching (MCB) process, thus solving the problem of low metal leaching efficiency from SLBs. Analysis of the underlying mechanism revealed that the effective extraction of metals from SLBs by the Fe2+-MCB process relied on Fe2+-releasing electrons to reduce refractory Co(III) to Co(II) that can be easily bioleached. Finally, the hazardous SLBs was transformed into a non-toxic material after treatment utilizing the Fe2+-MCB process. However, effective SLBs leaching was not achieved by the addition of Fe0 to the MCB system. Only 25% Co and 31% Li yields were obtained, as the addition of Fe0 caused acid consumption and bacterial apoptosis. Overall, this study revealed that reductants that cause acid consumption and harm bacteria should be ruled out for use in reductant-assisted bioleaching processes for extracting metals from SLBs.

Chemo-enzymatic functionalized sustainable cellulosic membranes: Impact of regional selectivity on ions capture and antifouling behavior.

Most of the polymeric membranes synthesized for decentralization of polluted water use fossil-based components. Thus, there is an urgent need to create robust and tunable nano/micro materials for confidently designing efficient and selective polymeric water filters with guaranteed sustainability. We have chosen a robust high-grade microfibrillated cellulose (MFC) as the functional material and selectively tuned it via enzymatic catalysis, which led to the attachment of phosphate group at the C6 position, followed by esterification (fatty acid attachment at C2 and C3 carbon), which led to the increase in its antifouling properties. We have demonstrated the robustness of the functionalization by measuring the separation of various metal ions, and the antifouling properties by adding foulants, such as Bovine Serum Albumin (BSA) and cancerous cells to the test solutions. These prototype affinity MFC membranes represent the most promising type of next-generation high-performance filtration devices for a more sustainable society.

Removal of heavy metal ion cobalt (II) from wastewater via adsorption method using microcrystalline cellulose-magnesium hydroxide.

Microcrystalline cellulose (MCC), magnesium sulfate hexahydrate, and trisodium citrate were reacted in ammonia bath in an aqueous solution to prepare a MCC-magnesium hydroxide (MH) composite adsorbent, which was used to adsorb heavy metal Co(II) ion. The method of using MCC-MH to adsorb and remove Co(II) was studied under different pH values, adsorbent dosages, contact times, initial Co(II) ion concentrations, and temperatures. The optimal process parameters include an MCC-MH dosage of 2.5 mg/mL, a contact reaction equilibrium time of 50 min, a Co(II) solution pH of 6.0-8.0, an initial Co(II) concentration of 300 mg/L, and a temperature of 303 K. The removal rate of Co(II) solution by MCC-MH was as high as 97.67%, and the maximum adsorption capacity of MCC-MH reached 153.84 mg/g under these optimal conditions. The adsorption isotherm of Co(II) conformed to the Langmuir model, the kinetic data of Co(II) conformed to the pseudo-second-order kinetic model, and the adsorption of Co(II) by MCC-MH was a spontaneous endothermic reaction under the optimized conditions. Analytical studies showed that Co(II) adsorption on MCC-MH composites is affected by chemical adsorption and involves the influence of intraparticle diffusion to a certain extent.

A basic and effective liquid phase microextraction with a novel automated mixing system for the determination of cobalt in quince samples by flame atomic absorption spectrometry.

A new, green, and simple liquid-phase microextraction method namely sieve conducted two syringe-based pressurized liquid-phase microextraction methods was combined with flame atomic absorption spectrometry for the preconcentration and determination of cobalt. For this aim, a novel automated syringe mixing system was developed to be used in the developed extraction procedure. Two syringes were connected to each other by an apparatus having six holes to produce efficient dispersion of the extractant. The pressure created between the two syringes by the forward and backward movements of the syringe plungers created an efficient dispersion of the extractant. In the present study, ligand as complexing agent was synthesized in our laboratory. Limits of detection and quantification were determined to be 1.8 and 6.0 µg L-1, respectively. A 33.7-fold enhancement in detection power was obtained with the developed method. Method was effectively applied for the determination of cobalt in quince samples.

Subcritical Water Extraction of Valuable Metals from Spent Lithium-Ion Batteries.

The leaching of valuable metals (Co, Li, and Mn) from spent lithium-ion batteries (LIBs) was studied using subcritical water extraction (SWE). Two types of leaching agents, hydrochloric acid (HCl) and ascorbic acid, were used, and the effects of acid concentration and temperature were investigated. Leaching efficiency of metals increased with increasing acid concentration and temperature. Ascorbic acid performed better than HCl, which was attributed to ascorbic acid's dual functions as an acidic leaching agent and a reducing agent that facilitates leaching reactions, while HCl mainly provides acidity. The chemical analysis of leaching residue by X-ray photoelectron spectroscopy (XPS) revealed that Co(III) oxide could be totally leached out in ascorbic acid but not in HCl. More than 95% of Co, Li, and Mn were leached out from spent LIBs' cathode powder by SWE using 0.2 M of ascorbic acid within 30 min at 100 °C, initial pressure of 10 bar, and solid-to-liquid ratio of 10 g/L. The application of SWE with a mild concentration of ascorbic acid at 100 °C could be an alternative process for the recovery of valuable metal in spent LIBs. The process has the advantages of rapid reaction rate and energy efficiency that may benefit development of a circular economy.

Usage of the newly synthesized poly(3-hydroxy butyrate)-b-poly(vinyl benzyl xanthate) block copolymer for vortex-assisted solid-phase microextraction of cobalt (II) and nickel (II) in canned foodstuffs.

The current research article was reported the synthesis of a novel poly(3-hydroxy butyrate)-b-poly(vinyl benzyl xanthate) block copolymer (PHB-Xa) for vortex-assisted solid-phase microextraction of cobalt(II) and nickel(II) from canned foodstuffs prior to their determinations by flame atomic absorption spectrometry. The block copolymer was synthesized and characterized by nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy. Experimental variables affecting the extraction efficiency of the copolymer were optimized. Since the PHB-Xa block copolymers have a high π conjugate structure and hydrophobicity, the use of this adsorbent yielded quantitative results for the extraction of Ni(II) and Co(II). After optimization, the linearities for Ni(II) and Co(II) were 0.05-80 ng mL-1 and 0.2-100 ng mL-1, respectively. The limits of detection and the limits of quantification were in the range of 0.015-0.06 ng mL-1 and 0.05-0.2 ng mL-1, respectively. The method was successfully applied to determination of Ni(II) and Co(II) in canned foodstuffs prepared by microwave digestion.

Isolation of a novel Co2+-resistant bacterium and the application of its siderophore in Co2+ recovery from an aqueous solution.

Siderophores are considered to have a good potential as decontamination agents owing to their metal-chelating abilities. In order to confirm whether siderophores can be used in the recovery of metal ions, a siderophore (or metallophore) exhibiting Co2+-chelating activity was screened to demonstrate its ability to recover Co2+ from an aqueous solution. A siderophore-producing bacterium, Pandoraea sp. HCo-4B, was identified from a screen of Co2+-resistant bacteria grown in an aerobic enrichment culture with a Co2+-supplemented medium. After incubation of the crude extracted siderophore in a Co2+-containing solution, the Co2+-siderophore complex was adsorbed on to a C18 column. The bound Co2+ was eluted from the column by the addition of 10 mM H2SO4. The recovered amount of Co2+ was proportional to the amount of the added siderophore. We observed that the siderophore identified in this study binds to Co2+ at a 1:1 ratio.

A green, accurate and sensitive analytical method based on vortex assisted deep eutectic solvent-liquid phase microextraction for the determination of cobalt by slotted quartz tube flame atomic absorption spectrometry.

Preconcentration of cobalt was carried out with deep eutectic solvent based liquid phase microextraction (DES-LPME) for trace determination by a slotted quartz tube (SQT) attached flame atomic absorption spectrometry (FAAS) system. Choline chloride and phenol in a 1:2 M ratio was used as a green solvent to extract cobalt from the aqueous sample solution. Key parameters influencing the extraction efficiency of cobalt were examined and optimized. Under the conditions optimized, the linear dynamic range was found between 5.0 and 50 µg L-1, and the limits of detection and quantification (LOD and LOQ) were calculated as 2.0 and 6.6 µg L-1, respectively. The detection power of the conventional FAAS was improved upon by 67 folds using the optimized DES-LPME-SQT-FAAS method. The developed analytical method was successfully applied for the determination of cobalt in linden tea samples and the recovery results obtained for different spiked concentrations (20, 30 and 40 µg L-1) were remarkable (≈100%).

Biorecovery of cobalt and nickel using biomass-free culture supernatants from Aspergillus niger.

In this research, the capabilities of culture supernatants generated by the oxalate-producing fungus Aspergillus niger for the bioprecipitation and biorecovery of cobalt and nickel were investigated, as was the influence of extracellular polymeric substances (EPS) on these processes. The removal of cobalt from solution was >90% for all tested Co concentrations: maximal nickel recovery was >80%. Energy-dispersive X-ray analysis (EDXA) and X-ray diffraction (XRD) confirmed the formation of cobalt and nickel oxalate. In a mixture of cobalt and nickel, cobalt oxalate appeared to predominate precipitation and was dependent on the mixture ratios of the two metals. The presence of EPS together with oxalate in solution decreased the recovery of nickel but did not influence the recovery of cobalt. Concentrations of extracellular protein showed a significant decrease after precipitation while no significant difference was found for extracellular polysaccharide concentrations before and after oxalate precipitation. These results showed that extracellular protein rather than extracellular polysaccharide played a more important role in influencing the biorecovery of metal oxalates from solution. Excitation-emission matrix (EEM) fluorescence spectroscopy showed that aromatic protein-like and hydrophobic acid-like substances from the EPS complexed with cobalt but did not for nickel. The humic acid-like substances from the EPS showed a higher affinity for cobalt than for nickel.

Selective removal of cobalt and copper from Fe (III)-enriched high-pressure acid leach residue using the hybrid bioleaching technique.

Removal of metals from high pressure acid leaching (HPAL) residue was essential to alleviate potential environmental threat and avoid valuable metals loss. However, cost-effective metals extraction from HPAL residue remains a difficulty. In this study, a hybrid bioleaching process was developed for Co and Cu extraction from HPAL residue of Cu-Co sulfide ores. Results for microbial community structure optimization showed that moderate thermophilum consortium with coexistence of iron oxidizer and sulfur oxidizer was more efficient on metal extraction compared with mesophiles. Further addition of citric acid, Fe (II) and S0 significantly enhanced the release of metals through improving the total biomass, attached cells and community diversity. As a result, 87.91% of cobalt and 58.52% of copper were extracted at initial pH 1.4 and pulp density of 50 g/L by hybrid bioleaching. The hazardous potential assessments revealed that the bioleached residue could be disposed safely. These findings demonstrated that organic acids assisting bioleaching with community adjusting was a promising strategy for metals removal from HPAL residue.

Method Development for Determining the Removal of Metals from the Water Column under Transformation/Dissolution Conditions for Chronic Hazard Classification.

An extension of the transformation/dissolution protocol (T/DP) was developed and evaluated as a tool to measure the removal of metals from the water column for chronic aquatic hazard classification. The T/DP extension (T/DP-E) consists of 2 parts: T/DP-E part 1, to measure metal removal from the water column via binding of metals to a substrate and subsequent settling, and T/DP-E part 2, to assess the potential for remobilization of metals following resuspension. The T/DP-E methodology (672-h [28-d] removal period, 1-h resuspension event, and 96-h resettling period) was tested using Cu, Co, and Sr solutions in the presence of a substrate. The metal removal rates varied from rapid removal for Cu to slower rates of removal for Co and Sr. The resuspension event did not trigger any increase in dissolved Cu, Co, or Sr. Additional 96-h experiments were conducted using dissolved Ni, Pb, Zn, and Ag and supported the conclusion that the T/DP-E is sufficiently robust to distinguish removal rates between metals with a wide range of reactivities. The proposed method provides a means to quantify the rate of metal removal from the water column and evaluate remobilization potential in a standardized and reliable way. Environ Toxicol Chem 2019;38:2032-2042. © 2019 SETAC.

Molecularly imprinted electroluminescence switch sensor with a dual recognition effect for determination of ultra-trace levels of cobalt (II).

A dual selection/recognition effect is described for cobalt (II) ions (Co2+). It is based on bovine serum albumin-metal-Co2+ coordination (BSA-Co2+) and the use of a molecularly imprinted polymer (MIP). An electrochemiluminescence (ECL) switch sensor was designed for detecting nanomolar levels of Co2+. The BSA-Co2+ coordination complex was chosen as a template to prepare a MIP modified switch sensor. The coordination reaction between BSA and Co2+ provides the first step in recognition, and MIP provides the second step for Co2+. This leads to a strong improvement in selectivity of the sensor. A multi-walled carbon nanotube/Cu nanoparticles/carbon quantum dots nanocomposite (MWCNT/Cu/C-dots) acts as an ECL device, and the BSA-Co2+ complex quenches the ECL signal. Therefore, the elution and resorption of BSA-Co2+ can be used as a switch to control ECL. Additionally, a method was established to detect Co2+, with the detection limit as low as 3.07 × 10-10 mol/L. The method was applied to the analysis of spiked environmental water, soil samples, and agricultural products. The recovery rates of the method were in the range of 87.5-111.3%.

Synthesis and application of sugarcane bagasse cellulose mixed esters. Part II: Removal of Co2+ and Ni2+ from single spiked aqueous solutions in batch and continuous mode.

Sugarcane bagasse cellulose succinate trimellitate (SBST) was prepared by a one-pot synthesis method. The synthesis of this novel mixed ester was investigated by a 23-factorial design. The parameters investigated were time, temperature, and succinic anhydride mole fraction (χSA). The responses evaluated were the adsorption capacity (qCo2+ and qNi2+), weight gain (wg), and number of carboxylic acid groups (nT,COOH). 13C Multiple Cross-Polarization solid-state NMR spectroscopy, 1H NMR relaxometry, and Fourier-transform infrared spectroscopy were used to elucidate the SBST structure. The best SBST reaction conditions were 100 °C, 660 min, and χSA of 0.2, which yielded SBST with a wg of 57.1%, nT,COOH of 4.48 mmol g-1, and qCo2+ and qNi2+ of 0.900 and 0.963 mmol g-1, respectively. The maximum adsorption capacities (Qmax) (pH 5.75, 25 °C) estimated by the Redlich-Peterson model for Co2+ and Ni2+ were 1.16 and 1.29 mmol g-1. The ΔadsH° values for Co2+ and Ni2+ adsorption obtained by isothermal titration calorimetry were 8.03 and 6.94 kJ mol-1. Regeneration and reuse of SBST were investigated and the best conditions applied for fixed-bed column adsorption in five consecutive cycles. SBST was fully desorbed and Qmax values for Co2+ (0.95 mmol g-1) and Ni2+ (1.02 mmol g-1) were estimated using the Bohart-Adams model.

Synthesis and application of sugarcane bagasse cellulose mixed esters. Part I: Removal of Co2+ and Ni2+ from single spiked aqueous solutions in batch mode using sugarcane bagasse cellulose succinate phthalate.

Sugarcane bagasse cellulose mixed ester succinate phthalate (SBSPh) was synthesized by a novel one-pot reaction method. The effects of temperature, time and mole fraction of succinic anhydride (χSA) on the responses weight gain (wg), number of carboxylic acid groups (nT,COOH), and adsorption capacity (q) of Co2+ and Ni2+ were evaluated by a 23 experimental design. The chemical structure of the material was elucidated by Fourier transform infrared, 13C Multiple Cross-Polarization solid-state NMR spectroscopy and 1H NMR relaxometry. The best SBSPh synthesis condition (100 °C, 11 h, χSA of 0.2) yielded a wg of 59.1%, nT,COOH of 3.41 mmol g-1, and values of qCo2+ and qNi2+ of 0.348 and 0.346 mmol g-1, respectively. The Sips model fitted better the equilibrium data, and the maximum adsorption capacities (pH 5.75 and 25 °C) estimated by this model were 0.62 and 0.53 mmol g-1 for Co2+ and Ni2+, respectively. The ΔadsH° values estimated by isothermal titration calorimetry were 8.43 and 7.79 kJ mol-1 for Co2+ and Ni2+, respectively. Desorption and re-adsorption efficiencies were evaluated by a 22 experimental design, which showed that SBSPh adsorbent can be recovered and reused without significant loss of adsorption capacity.

Fabrication and characterization of composite cryobeads based on chitosan and starches-g-PAN as efficient and reusable biosorbents for removal of Cu2+, Ni2+, and Co2+ ions.

Novel composite biosorbents were developed in this work as cryobeads by dual cross-linking of a mixture of chitosan (CS) and starch coming from different botanical sources, such as potato, wheat, and rice, grafted with poly(acrylonitrile) (PAN). Glutaraldehyde and poly(ethylene glycol diglycidyl ether) were used as cross-linkers. Composite cryobeads were characterized by FTIR, SEM-EDX, and swelling kinetics. Sorption of Cu2+, Ni2+, and Co2+ onto the novel biosorbents was investigated as a function of time and the concentration of the metal ion, at the optimum pH and sorbent dose. Pseudo-second-order kinetic model and Elovich model well fitted the kinetic results, indicating chemisorption as the most probable mechanism of sorption, while the Langmuir, and Sips isotherm models described the sorption at equilibrium for all metal ions. The values of the maximum sorption capacity of Cu2+, Ni2+, and Co2+ onto the composite sorbent based on CS and rice starch-g-PAN were as follows: 100.6 mg/g, 83.25 mg/g, and 74.01 mg/g, respectively. The nitrile groups present in the biocomposites CS/starch-g-PAN constitute a source to further increase the sorption capacity by their hydrolysis. A remarkable level of reusability was found for the composite cryobeads, no decrease of the sorption capacity being observed after five consecutive sorption/desorption cycles.

Performance of ceria/iron oxide nano-composites based on chitosan as an effective adsorbent for removal of Cr(VI) and Co(II) ions from aqueous systems.

A novel chitosan/ceria/iron oxide (CS/ceria/Fe3O4) nano-composite adsorbent was synthesized for removal of Cr(VI) and Co(II) ions from aqueous systems in a batch system. The adsorbents were characterized by field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), and Brunauer- Emmett-Teller (BET) analyses. The behavior of swelling kinetics was also studied. The effect of several adsorption parameters including CeO2 and Fe3O4 contents, initial pH, contact time, initial Cr(VI) and Co(II) concentration, and temperature on the adsorption capacity was studied. The double exponential model revealed a better fit with the kinetic data of Cr(VI) and Co(II) ions. The Cr(VI) and Co(II) adsorption process well fitted the Langmuir model. The maximum adsorption capacities estimated from Langmuir isotherm model were 315.4 and 260.6 mg/g for Cr(VI) and Co(II) ions, respectively. Also, thermodynamic parameters were used to distinguish the nature of Cr(VI) and Co(II) adsorption. The reusability of CS/ceria/Fe3O4 nano-composite was evaluated with stripping agents of 0.1 M NaOH and 0.1 M HNO3. Finally, the evaluation of Cr(VI)-Co(II) coexisting system confirmed that the presence of Co(II) ions played an inhibitor role on the Cr(VI) adsorption.

Spent MgO-carbon refractory bricks as a material for permeable reactive barriers to treat a nickel- and cobalt-contaminated groundwater.

Spent magnesia (MgO)-carbon refractory bricks were repurposed as a permeable reactive barrier reactive media to treat a nickel (5 mg l-1)- and cobalt (0.3 mg l-1)-contaminated groundwater. MgO has been used for decades as a heavy metal precipitating agent as it hydrates and buffers the pH in a range of 8.5-10 associated with the minimum solubility of various divalent metals. The contaminated groundwater site's conditions are typical of contaminated neutral drainage with a pH of 6 as well as high concentrations of iron (220 mg l-1) and sulphates (2500 mg l-1). Using synthetic contaminated water, batch and small-scale column tests were performed to determine the treatment efficiency and longevity. The increase and stabilization of the pH at 10 observed during the tests are associated with the hydration and dissolution of the MgO and promoted the removal not only of a significant proportion of the contaminants but also of iron. During the column test, this accumulation of precipitates over time clogged and passivated the MgO resulting in a loss of chemical performance (pH lowering, metal breakthrough) after 210 pore volumes of filtration. Precipitation also affected the hydraulic conductivity values which dropped from 2.3·10-3 to 4.2·10-4 m s-1 at the end of test. Saturation indices and XRD analyses suggest the precipitates formed are likely composed of goethite as well as iron, cobalt and nickel hydroxides. Recycled MgO-C refractory bricks were demonstrated to be an efficient reactive material for the removal of Co and Ni, but careful considerations should be taken of the potential clogging and passivation phenomena given particular physicochemical conditions.

Removal of cobalt and lead ions from wastewater samples using an insoluble nanosponge biopolymer composite: adsorption isotherm, kinetic, thermodynamic, and regeneration studies.

In this study, an insoluble nanosponge biopolymer composite was synthesized, using a combined process of amidation reaction, cross-linking polymerization, and sol-gel method to obtain a phosphorylated multiwalled carbon nanotube-cyclodextrin/silver-doped titania (pMWCNT-ßCD/TiO2-Ag). This work mainly emphasized on the removal of lead (Pb2+) and cobalt (Co2+) metal ions from synthetic and real wastewater samples using the synthesized pMWCNT-ßCD/TiO2-Ag as a biosorbent. The new material was characterized by Fourier transform infrared (FTIR) spectroscopy, zeta potential, Brunauer-Emmett-Teller (BET) method, and scanning electron microscopy (SEM). Adsorption studies for the model pollutants were performed in batch mode. The effect of the solution pH, adsorbent dosage and the presence of competiting ions were investigated. The isotherm, kinetic, thermodynamic, and regeneration studies were also undertaken. The ability of the new material to effectively remove Pb2+ and Co2+ from synthetic wastewater and mine effluent samples was tested. The maximum removal capacities achieved for the removal of Pb2+ and Co2+ from mine effluent sample were 35.86 and 7.812 mg/g, respectively.