Recovery of Li, Ni, Co and Mn from spent lithium-ion batteries assisted by organic acids: Process optimization and leaching mechanism

The proper recycling of spent lithium-ion batteries(LIBs)can promote the recovery and utilization of valuable resources,while also negative environmental effects resulting from the presence of toxic and hazardous substances.In this study,a new environmentally friendly hydro-metallurgical process was proposed for leaching lithium(Li),nickel(Ni),cobalt(Co),and manganese(Mn)from spent LIBs using sulfuric acid with citric acid as a reductant.The effects of the concentration of sulfuric acid,the leaching temperature,the leaching time,the solid-liquid ratio,and the reducing agent dosage on the leaching behavior of the above elements were investigated.Key parameters were optimized using response surface methodology(RSM)to maximize the recovery of metals from spent LIBs.The maxim-um recovery efficiencies of Li,Ni,Co,and Mn can reach 99.08%,98.76%,98.33%,and 97.63%.under the optimized conditions(the sulfuric acid concentration was 1.16 mol/L,the citric acid dosage was 15wt%,the solid-liquid ratio was 40 g/L,and the temperature was 83℃ for 120 min),respectively.It was found that in the collaborative leaching process of sulfuric acid and citric acid,the citric acid initially provided strong reducing CO_(2)^(-),and the transition metal ions in the high state underwent a reduction reaction to produce transition metal ions in the low state.Additionally,citric acid can also act as a proton donor and chelate with lower-priced transition metal ions,thus speeding up the dissolution process.

Citric and Oxalic Acids Effect on Pb and Zn Uptake by Maize and Winter Wheat

A pot experiment was conducted to investigate the influence of citric and oxalic acids effect on Pb and Zn uptake by corn and winter wheat. The experiment was employed with citric acid (CA) applied at 3 rates (0, 1.5 and 3.0 mmol kg-1 soil), oxalic acid (OA) at 3 rates (0, 1.5 and 3.0mmol kg-1 soil) and citric acid combined with oxalic acid (1.5 mmol citric acid combined with 1.5 mmol oxalic acid kg-1). Two types of soil were chose in the experiment. One was collected from the agricultural soil near a battery-recycling factory in Anhui province, China (site A) and the other was collected from a Pb-Zn mine residues in Hunan province, China (site B). The results showed that soil pH varied with the different treatment of citric and oxalic acids. However, there were no differences in all the treatments. 3.0mmol CA kg-1 soil addition significantly increased the concentrations of the CaCI2-extractable Pb and Zn and other treatments have no significantly increased. The highest shoot concentrations of Pb and

Corrosion resistance of Mg-Al-LDH steam coating on AZ80 Mg alloy:Effects of citric acid pretreatment and intermetallic compounds

In this study,the effects of intermetallic compounds(Mg_(17)Al_(12)and Al_(8)Mn_(5))on the Mg-Al layered double hydroxide(LDH)formation mechanism and corrosion behavior of an in-situ LDH/Mg(OH)_(2)steam coatings on AZ80 Mg alloy were investigated.Citric acid(CA)was used to activate the alloy surface during the pretreatment process.The alloy was first pretreated with CA and then subjected to a hydrothermal process using ultrapure water to produce Mg-Al-LDH/Mg(OH)_(2)steam coating.The effect of different time of acid pretreatment on the activation of the intermetallic compounds was investigated.The microstructure and elemental composition of the obtained coatings were analyzed using FE-SEM,EDS,XRD and FT-IR.The corrosion resistance of the coated samples was evaluated using different techniques,i.e.,potentiodynamic polarization(PDP),electrochemical impedance spectrum(EIS)and hydrogen evolution test.The results indicated that the CA pretreatment significantly influenced the activity of the alloy surface by exposing the intermetallic compounds.The surface area fraction of Mg_(17)Al_(12)and Al_(8)Mn_(5)phases on the surface of the alloy was significantly higher after the CA pretreatment,and thus promoted the growth of the subsequent Mg-Al-LDH coatings.The CA pretreatment for 30 s resulted in a denser and thicker LDH coating.Increase in the CA pretreatment time significantly led to the improvement in corrosion resistance of the coated AZ80 alloy.The corrosion current density of the coated alloy was lower by three orders of magnitude as compared to the uncoated alloy.

Preparation and Performance of Chitosan/Citric Acid Modified Magnesium Oxychloride Cement

Citric acid(CA)and chitosan(CS)were employed to modify magnesium oxychloride cement(MOC).Multiscale measurements were implemented to study the properties of the modified MOC pastes.Results show that the addition of CA/CS significantly changes the content of each phase and the microstructure of phase 5.The single addition of CA can effectively increase the compressive strength of MOC after 7 d curing,while CS exerts no obvious effect on the compressive strength.As to the simultaneous addition of CA and CS,the compressive strength of MOC gradually decreases with the increasing content of CS.Interestingly,mixing CA and CS significantly enhances the water resistance of MOC and decreases the degradation rate of MOC in phosphate buffered solution,which can be ascribed to the low specific surface area of the plate-like crystals in the modified MOC and the reduction of pores in the structure.

MUF Resins Improved by Citric Acid as Adhesives for Wood Veneer Panels

This article presents the first applied results of using citric acid in combinations with a melamine-urea-formal-dehyde(MUF)resin for bonding wood veneers.The chemical reactions involved are shown based on a MALDI ToF analysis of the reaction of the MUF resin with citric acid.The preliminary results of the physical and mechanical properties of the LVL prepared are also presented.Veneers from Populus sp were used to manufacture 5-layer laminated veneer lumber(LVL)of small dimensions.Five combinations of the amount of citric acid,MUF spread rate and pressing parameters were tested.LVL bonded with 20%of citric acid+100 g/m^(2)of MUF,hot-pressed using a 3-step process with maximum 1.5 MPa of pressure yielded the board with better dimensional stability and mechanical properties.It could be concluded that citric acid in combination with MUF can be used for bonding wood veneer and the research should be continued to study further the parameters involved and to enhance the results.

Comparative Effect of Adding Synthetic Citric Acid to Natural Lemon Juice (Citrus aurantiifolia) on the Stability of Hibiscus Drinks Stored at 4°C and 37°C

The general objective of the work is to compare the effect of the addition of synthetic citric acid compared to the addition of natural fruit juice of Citrus aurantiifolia on the conservation of drink based on red chalice H. sabdariffa. The tests were carried out over a period of 5 weeks at 4°C and 37°C with seven batches of beverage samples prepared at the rate of a calyx/water ratio of 1/40 (kg·kg-1) and added respectively citric acid at 1, 2 and 4 g·L-1 and lemon juice at 10, 20 and 40 mL·L-1. The characterization of the different batches of beverages was carried out from day one. A follow-up of the residual anthocyanin content and the intensity of the red coloring were carried out over five weeks. The anthocyanin concentration was determined by the pH-differential method. The red color degradation index is determined based on the CIELAB color system (L*, a*, b* and L*). R and Minitab 18 software was used for data processing. The results of the monitoring of the parameters showed that the concentration of 1 g AC L-1 retains 2.7 mg more of the anthocyanins than adding 10 mL JC L-1 and longer maintains red color when stored at 4°C and 37°C/5 weeks. The 2 g AC L-1 and 4 g AC L-1 ratios have the same effects as the addition of 20 and 40 mL of lemon juice, all accelerating the degradation of anthocyanins and the red color. After 5 weeks of storage at 37°C, the effect of the temperature combined with the increase in the acidity of the samples (2 to 4 g AC L-1 and 20 to 40 ml JC L-1), have accelerated the total disappearance of the red color on all samples.

Corrosion protection of AZ91D magnesium alloy by a cerium-molybdenum coating-The effect of citric acid as an additive

In order to improve the corrosion resistance of AZ91D magnesium alloy,a coating was formed by a potentiostatic technique from a solutions containing Ce(NO_(3))_(3),Na_(2)MoO_(4)and citric acid(H_(3)Cit).The degree of corrosion protection achieved was evaluated in simulated physiological solution by monitoring the open circuit potential,polarization techniques and electrochemical impedance spectroscopy(EIS).Surface analysis techniques(SEM,EDS,X-ray diffraction and X-ray photoelectron spectroscopy(XPS))were used for coating characterization.The film is mainly composed by cerium and molybdenum oxides and magnesium oxides and hydroxides.The obtained results show that the corrosion resistance of the coated electrodes has been increased significantly.This improvement in the anticorrosive performance is in part due to the corrosion inhibition properties of H_(3)Cit.

Effects of Citric Acid on Hydration Process and Mechanical Properties of Thermal Decomposed Magnesium Oxychloride Cement

In order to make full use of salt lake magnesium resources and improve the strength of the thermal decomposed magnesium oxychloride cement （TDMOC）, the effects of citric acid on the hydration process and mechanical properties of TDMOC was studied. The hydration heat release at initial 24 h and strengths at 3, 7, and 28 days of TDMOC specimens were conducted. The hydration products and paste microstructure were analyzed by XRD, FT-IR and SEM, respectively. The results showed that citric acid can not only reduce the 24 h hydration heat release and delay the occurring time of second peak of TDMOC, but also produce more 5Mg（OH）z.MgC12.SH20 and less Mg（OH）2 in hydration process of TDMOC. More perfect and slender crystals were observed in the microstructure of the TDMOC pastes with citric acid. The results demonstrated that citric acid as an additive of TDMOC can decrease the hydration heat release and increase the compressive strength and flexural strength of TDMOC. The possible mechanism for the strength enhancement was discussed.

Investigation on leaching of malachite by citric acid

Leaching of an oxidized copper ore containing malachite, as a new approach, was investigated by an organic reagent, citric acid. Sulfuric acid is the most common reagent in the leaching of oxide copper ores, but it has several side effects such as severe adverse impact on the environment. In this investigation, the effects of particle size, acid concentration, leaching time, solid/liquid ratio, temperature, and stirring speed were optimized. According to the experimental results, malachite leaching by citric acid was technically feasible. Optimum leaching conditions were found as follows： the range of particle size, 105-150 μm; acid concentration, 0.2 M; leaching time, 30 min; solid/liquid ratio, 1：20 g/mL; temperature, 40℃; and stirring speed, 200 r/min. Under the optimum conditions, 91.61% of copper was extracted.

Wheat straw biochar amendment suppresses tomato bacterial wilt caused by Ralstonia solanacearum: Potential effects of rhizosphere organic acids and amino acids

Complex interactions based on host plant, rhizosphere microorganisms and soil microenvironment are presumed to be responsible for the suppressive properties of biochar against soil-borne diseases, although the underlying mechanisms are not well understood. This study is designed to evaluate the efficacy of biochar amendment for controlling tomato bacterial wilt caused by Ralstonia solanacearum, and to explore the interactions between biochar-induced changes in rhizosphere compound composition, the pathogen and tomato growth. The results showed that biochar amendment decreased disease incidence by 61–78% and simultaneously improved plant growth. The positive ‘biochar effect' could be associated with enhanced microbial activity and alterations in the rhizosphere organic acid and amino acid composition. Specifically, elevated rhizosphere citric acid and lysine, but reduced salicylic acid, were induced by biochar which improved microbial activity and rendered the rhizosphere unsuitable for the development of R. solanacearum. In addition, nutrients which were either made more available by the stimulated microbial activity or supplied by the biochar could improve plant vigor and potentially enhance tomato resistance to diseases. Our findings highlight that biochar's ability to control tomato bacterial wilt could be associated with the alteration of the rhizosphere organic acid and amino acid composition, however, further research is required to verify these ‘biochar effects' in field conditions.

Novel neuroprotective and hepatoprorective effects of citric acid in acute malathion intoxication

Objective: To study the effect of citric acid given alone or combined with atropine on brain oxidative stress, neuronal injury, liver damage, and DNA damage of peripheral blood lymphocytes induced in the rat by acute malathion exposure. Methods: Rats were received intraperitoneal(i.p.) injection of malathion 150 mg/kg along with citric acid(200 or 400 mg/kg, orally), atropine(1 mg/kg, i.p.) or citric acid 200 mg/kg+atropine 1 mg/kg and euthanized 4 h later. Results: Malathion resulted in increased lipid peroxidation(malondialdehyde) and nitric oxide concentrations accompanied with a decrease in brain reduced glutathione, glutathione peroxidase(GPx) activity, total antioxidant capacity(TAC) and glucose concentrations. Paraoxonase-1, acetylcholinesterase(ACh E) and butyrylcholinesterase activities decreased in brain as well. Liver aspartate aminotransferase and alanine aminotransferase activities were raised. The Comet assay showed increased DNA damage of peripheral blood lymphocytes. Histological damage and increased expression of inducible nitric oxide synthase(i NOS) were observed in brain and liver. Citric acid resulted in decreased brain lipid peroxidation and nitric oxide. Meanwhile, glutathione, GPx activity, TAC capacity and brain glucose level increased. Brain ACh E increased but PON1 and butyrylcholinesterase activities decreased by citric acid. Liver enzymes, the percentage of damaged blood lymphocytes, histopathological alterations and i NOS expression in brain and liver was decreased by citric acid. Meanwhile, rats treated with atropine showed decreased brain MDA, nitrite but increased GPx activity, TAC, ACh E and glucose. The drug also decreased DNA damage of peripheral blood lymphocytes, histopathological alterations and i NOS expression in brain and liver. Conclusions: The study demonstrates a beneficial effect for citric acid upon brain oxidative stress, neuronal injury, liver and DNA damage due to acute malathion exposure.

CROSS-LINKING OF CHITOSAN WITH GLUTARALDEHYDE IN THE PRESENCE OF CITRIC ACID——A NEW GELLING SYSTEM

The procedure for preparing a new type of uniform and porous chitosan gel from citric acid medium is described. Its swelling behavior in different media was compared with those of the gels prepared by other methods. The ultrastructure of the xerogel prepared from citric acid was characterized using electron microscopy (SEM).

Synthesis of Mesoporous, Nanocrystalline Lanthanum Phosphate in the Presence of Citric Acid and Stearic Acid

Lanthanum phosphate was prepared in the presence of citric acid and stearic acid under methanolic conditions at pH 4.5 and pH 7, respectively. The samples obtained were intensively characterized using X-ray diffraction, nitrogen adsorption-desorption isotherm study, transmission electron microscopy （TEM）, thermal gravimetric and differential thermal analysis, and Fourier transform infrared （FTIR） analysis . The as-synthesized samples prepared at pH 4.5 showed lamellar mesostruroned form with high crystallinity. Results showed that the pore size and pore volume changed when the materials were prepared under different pH conditions. Morphology of the samples was observed by using TEM, which showed that the samples possessed relatively small particles closely packed together. The as-synthesized samples were investigated using FTIR, and the mesopore formation mechanism was discussed.

Novel Ni/CeO_2-Al_2O_3 composite catalysts synthesized by one-step citric acid complex and their performance in catalytic partial oxidation of methane

A series of novel Ni/CeOe-Al2O3 composite catalysts were synthesized by one-step citric acid complex method, The as-synthesized catalysts were characterized by N2 physical adsorption/desorption, X-ray diffraction （XRD）, Fourier transform infrared （FT-IR） spectroscopy, hydrogen temperature-programmed reduction （Hz-TPR）, X-ray photoelectron spectroscopy （XPS） and thermogravimetry analysis （TGA）. The effects of nickel content, calcination and reaction temperatures, gas hourly space velocity （GHSV） and inert gas dilution of N2 on their performance of catalytic partial oxidation of methane （CPOM） were investigated. Catalytic activity test results show that the highest methane conversion （〉85%）, the best selectivities to carbon monoxide （〉87%） and to hydrogen （〉95%）, the excellent stability and perfect Hz/CO ratio （2.0） can be obtained over Ni/CeO2-Al2O3 with 8 wt% Ni content calcined at 700 ℃ under the reaction condition of 750 ℃, CH4/O2 ratio of 2 ： 1 and gas hourly space velocity of 12000 mL.h-1 .g-1. Characterization results show that the good catalytic performance of this composite catalyst can be contributed to its large specific surface area （~108 m2.g-1）, small crystallite size, easy reducibility and low coking rate.

Pediatric bowel preparation: Sodium picosulfate, magnesium oxide, citric acid vs polyethylene glycol, a randomized trial

BACKGROUND Bowel preparation in children can be challenging.AIM To describe the efficacy, safety, and tolerability of sodium picosulfate, magnesium oxide, and citric acid(SPMC) bowel preparation in children.METHODS Phase 3, randomized, assessor-blinded, multicenter study of low-volume, divided dose SPMC enrolled children 9-16 years undergoing elective colonoscopy. Participants 9-12 years were randomized 1:1:1 to SPMC ? dose × 2, SPMC 1 dose × 2, or polyethylene glycol(PEG). Participants 13-16 years were randomized 1:1 to SPMC 1 dose × 2 or PEG. PEG-based bowel preparations were administered per local protocol. Primary efficacy endpoint for quality of bowel preparation was responders(rating of ‘excellent' or ‘good') by modified Aronchick Scale. Secondary efficacy endpoint was participant's tolerability and satisfaction from a 7-item questionnaire. Safety assessments included adverse events(AEs) and laboratory evaluations.RESULTS 78 participants were randomized, 48 were 9-12 years, 30 were 13-16 years. For the primary efficacy endpoint in 9-12 years, 50.0%, 87.5%, and 81.3% were responders for SPMC ? dose × 2, SPMC 1 dose × 2, and PEG groups, respectively. Responder rates for 13-16 years were 81.3% for SPMC 1 dose × 2 and 85.7% for PEG. Overall, 43.8% of participants receiving SPMC 1 dose × 2 reported it was ‘very easy' or ‘easy' to drink, compared with 20.0% receiving PEG. Treatment-emergent AEs were reported by 45.5% of participants receiving SPMC 1 dose × 2 and 63.0% receiving PEG.CONCLUSION SPMC was an efficacious and safe for bowel preparation in children 9-16 years, with comparable efficacy to PEG. Tolerability for SPMC was higher compared to PEG.

The Mechanism of Sol-Gel Synthesis of Normal Spinel LiMn_2O_4 with Chelation of Citric Acid

The sol-gel process of citric acid chelating with metal cations for the synthesis of normal spinel LiMn 2O 4 and the reaction mechanism were investigated by means of XRD,IR,TG-DTA, and SEM.The results show that at the beginning lithium citrate and chelate compound of citric acid with manganese ions formed,and then with heating the esterification and condensation reactions occured between them and glycol.The products obtained are polymers in which metal cations are distributed homogeneously on atomic scale that ensure high reactivity to cations of Li + and Mn 2+.Firing the gel prepared by this process,the lattice diffusions of solid reactant ions caused by non-homogeneity of reactants are eliminated and avoided.At 400℃ phase-pure LiMn 2O 4 with nanometer scale crystallization having precise stoichiometry and perfect crystallization can be obtained.The model of chelate coordinate of double-molecule between citric acid and Mn 2+ in the gel network is proposed.It is important for explaining the dispersion state of Mn 2+ and the formation process of gel by this model.

Improved flotation performance of hematite fines using citric acid as a dispersant

In this study, citric acid was used as a dispersant to improve the flotation performance of hematite fines. The effect and mechanism of citric acid on the reverse flotation of hematite fines were investigated by flotation tests, sedimentation experiments, scanning electron microscopy（SEM）, zeta-potential measurements, and X-ray photoelectron spectroscopy（XPS）. The results of SEM analysis and flotation tests reveal that a strong heterocoagulation in the form of slime coating or coagulation in hematite fine slurry affects the beneficiation of hematite ores by froth flotation. The addition of a small amount of citric acid（less than 300 g/t） favorably affects the reverse flotation of hematite fines by improving particle dispersion. The results of sedimentation experiments, zeta-potential measurements, and XPS measurements demonstrate that citric acid adsorbs onto hematite and quartz surfaces via hydrogen bonding, thereby reducing the zeta potentials of mineral surfaces, strengthening the electrical double-layer repulsion between mineral particles, and dispersing the pulp particles.

Catalytic-kinetic spectrophotometric determination of vanadium (V) based on the Celestine blue-bromate-vanadium (V)-citric acid reaction

A novel sensitive and relatively selective kinetic method is presented for the determination of V（V） based on its catalytic effect on the oxidation reaction of Celestine blue by potassium bromate in the presence of citric acid as an activator. The reaction was monitored spectropho- tometrically by measuring the decrease in absorbance of Celestine blue at a maximum absorption wavelength of 540 nm between 0.5 and 9 min （the fixed-time method） in an H3PO4 medium at 45℃. The effect of various parameters such as concentrations of H3PO4, citric acid, potassium bromate and Celestine blue, ionic strength, reaction temperature and time on the rate of V（V） catalyzed reaction was studied. The method is free from the most interferences, especially from large amounts of V（IV）. The decrease in absorbance is proportional to the concentration of V（V） over the entire concentration range tested （0.025-1.25 lag.mL^-1） with a detection limit of 6.80 tag.L^-1 （according to statistical 3Sblank/k criterion） and a coefficient of variation （CV） of 1.78% （for ten replicate measurements at 95% confidence level）. The proposed method suffers from a few interferences such as Cr（VI） and Hg（Ⅱ） ions. The method was successfully applied to the determination of V（V） in river water, lake water, tap water, natural drinking water samples and a certified standard reference material such as SRM-1640 with satis- factory results. The vanadium contents of natural water samples were detected by using both linear calibration curve and standard addition curve methods. The recoveries of spiked vanadium （V） into the certified standard water sample were found to be quantitative, and the reproducibility was satisfactory. It was observed that the results of the SRM 1640 were in good agreement with the certified value.

Effect of Wheat Middlings, Microbial Phytase, and Citric Acid on Phytate-Phosphorus, Calcium, and Protein Utilization of Broilers

A corn-soybean meal diet （CSB） （or Diet 1） containing 23% crude protein （CP） was used as the positive control, and another corn-soybean meal diet containing 21% CP and 15% wheat middlings （WM） （or Diet 2） was used as the basal diet, which was treated with four different treatments. Digestibility experiment was employed to discuss the collective effect of citric acid, and intrinsic and microbial phytase. By comparing and analyzing effects of them in the low-nutrient broiler diets, the results showed five treatments had similar effects on Tibia ash （%） （mg） （P〉0.05）. Under the supplementation of bacterial phytase or citric acid, the daily body weight gain （ADG）, gain：feed （G：F） ratio, and calcium （Ca） utilization were similar to that of standard-nutrient CSB diet （Diet 1） （P 〉 0.05）. And, fecal phosphorus （P） and CP utilization were lower than （P〈0.05） that of Diet 1. But P utilization was significantly higher than （P〈0.01） that of Diet 1. However, the ADG, G：F, and CP utilization produced by supplementation of intrinsic phytase were lower than those of Diet 1, but other aspects were similar to those produced by Diet 1 （P〉0.05）. In Diet 5, citric acid, intrinsic and bacterial phytase were added to the diet, which produced a 1.4% decrease on fecal P, a 7.2% increase on Ca utilization, which was significantly higher than （P〈0.01） those of the other four Diets, a 3.9% increase on G：F, which was similar to that of Diet 1, and a 2.3% increase on CP utilization, which was higher than （P〈0.05） that of the other three diets. In summary, the results of this study indicated that citric acid, intrinsic and bacterial phytase might have some additive or synergistic effects, and low-nutrient CSB diets with 15% wheat middlings, 750 U kg^-1 phytase, and 3% citric acid might substitute completely for standard CSB in broilers.

Influence of sulfur doping on the molecular fluorophore and synergistic effect for citric acid carbon dots

In citric acid-based carbon dots,molecular fluorophore contributes greatly to the fluorescence emission.In this paper,the nitrogen and sulfur co-doped carbon dots(N,S-CDs)were prepared,and an independent sulfur source is selected to achieve the doping controllability.The influence of sulfur doping on the molecular fluorophore was systematically studied.The introduction of sulfur atoms may promote the formation of molecular fluorophore due to the increased nitrogen content in CDs.The addition surface states containing sulfur were produced,and S element exists as-SO_(3),and-SO_(4)groups.Appreciate ratio of nitrogen and sulfur sources can improve the fluorescence emission.The photoluminescence quantum yields(PLQY)is increased from 56.4%of the single N-doping CDs to 63.4%of double-doping CDs,which ascribes to the synergistic effect of molecular fluorophores and surface states.The sensitivity of fluorescence to pH response and various metal ions was also explored.