Kinetics of leaching lithium from lepidolite using mixture of hydrofluoric and sulfuric acid

The fluorine-based chemical method shows great potential in leaching lithium(Li) from lepidolite. Leaching kinetics of Li in a mixture of sulfuric acid and hydrofluoric acid, which is a typical lixivant for the fluorine-based chemical method, was carried out under crucial factors such as different HF/ore ratios(1:1-3:1 g/mL) and leaching temperatures(50-85℃). The kinetics data fit well with the developed shrinking-core model, indicating that the leaching rate of Li was controlled by the chemical reaction and inner diffusion at the beginning of leaching(0-30 min) as a calculated apparent activation energy(Ea) of 20.62 kJ/mol. The inner diffusion became the rate-limiting step as the leaching continues(60-180 min). Moreover, effects of HF/ore ratio and leaching temperature on selective leaching behavior of Li, Al and Si were discussed. 90% of fluorine mainly existed as HF/F-in leaching solution, which can provide theoretical guidance for further removal or recovery of F.

Alpha radiolysis of nitric acid aqueous solution irradiated by 238Pu source

Alpha radiolysis of nitric acid aqueous solution by a ^(238)Pu source is investigated experimentally and theoretically.The time dependence of the nitrous acid yield on dose rate,nitric acid concentration,and nitrate ion concentration is studied.A novel kinetic model for the α-radiolysis of nitric acid aqueous solution is established,by considering the direct and indirect effects.The simulation results agree well with the experimental data,indicating the validity of our model to treat the reaction paths for generation and consumption of nitrous acid.It is shown that the redox reactions involving Pu cannot be neglected in theα-radiolysis of the solution.The results provide a better understanding of the α-ray radiolysis of aqueous nitric acid.

Cross-talk between calcium-calmodulin and nitric oxide in abscisic acid signaling in leaves of maize plants

Using pharmacological and biochemical approaches, the signaling pathways between hydrogen peroxide （H2O2）, calcium （Ca^2＋）-calmodulin （CAM）, and nitric oxide （NO） in abscisic acid （ABA）-induced antioxidant defense were investigated in leaves of maize （Zea mays L.） plants. Treatments with ABA, H2O2, and CaCl2 induced increases in the generation of NO in maize mesophyll cells and the activity of nitric oxide synthase （NOS） in the cytosolic and microsomal fractions of maize leaves. However, such increases were blocked by the pretreatments with Ca^2＋ inhibitors and CaM antagonists. Meanwhile, pretreatments with two NOS inhibitors also suppressed the Ca^2＋-induced increase in the production of NO. On the other hand, treatments with ABA and the NO donor sodium nitroprusside （SNP） also led to increases in the concentration of cytosolic Ca^2＋ in protoplasts of mesophyll cells and in the expression of calmodulin 1 （CaM1） gene and the contents of CaM in leaves of maize plants, and the increases induced by ABA were reduced by the pretreatments with a NO scavenger and a NOS inhibitor. Moreover, SNP-induced increases in the expression of the antioxidant genes superoxide dismutase 4 （SOD4）, cytosolic ascorbate peroxidase （cAPX）, and glutathione reductase 1 （GR1） and the activities of the chloroplastic and cytosolic antioxidant enzymes were arrested by the pretreatments with Ca^2＋ inhibitors and CaM antagonists. Our results suggest that Ca^2＋-CaM functions both upstream and downstream of NO production, which is mainly from NOS, in ABA- and H2O2-induced antioxidant defense in leaves of maize plants.

Influence of Nitric Acid Concentration on Characteristics of Olive Stone Based Activated Carbon

In this work we investigated the effect of nitric acid concentration on the pore structure,surface chemistry and liquid phase adsorption of olive stone based activated carbon prepared by mixing process using phosphoric acid and steam as activating agents.Chemicals and textural characterization show that the increase of HNO3concentration increases considerably the total acidic groups but decreases specific surface area and pore volume.The study of adsorption in aqueous solutions of two organics,phenol and methylene blue,on raw and oxidized activated carbon indicates that the treatment of mixed activated carbon with different concentrations of nitric acid improves the adsorbent capacity for methylene blue at HNO3concentrations less or equal to 2 mol·L 1,while it has a negative effect on phenol adsorption.

Microwave pretreatment for enhanced selective nitric acid pressure leaching of limonitic laterite

As clean energy,the microwave is commonly used to pretreat various ores.In this work,the microwave dielectric properties of limonitic laterite ore were measured by resonant cavity perturbation technique and the effects from microwave were systematically investigated.Results indicated that limonitic laterite had high microwave absorbance.After microwave pretreatment,the microstructure of the laterite became less aggregated and more porous and the main phase transformed from goethite to hematite that improved leaching in nitric acid(1.2 kg HNO3/kg ore);Ni,Co,Fe,and Mg extraction ratios were 95.2%,98.1%,1.8%and 15%,respectively,after leaching for 60 min at 200°C and 500 r/min.Furthermore,in the process of goethite to hematite by microwave pretreatment,the nickel-containing mineral is activated,which makes nickel be leached easily.The leaching process has high Ni extraction ratio compared to that without microwave(82%)and conventional pretreatment(90.4%).Therefore,microwave pretreatment of limonitic laterite before nitric acid pressure leaching is an effective way to improve the selectivity and extraction of the leach.

Coordination leaching of tungsten from scheelite concentrate with phosphorus in nitric acid

A hydrometallurgical process for tungsten extraction and recovery from scheelite is reported.The technology includes leaching scheelite using phosphoric acid as chelating agent in nitric acid solutions,extracting tungsten by solvent extraction and reusing leaching agent.In the leaching process,affecting factors,such as temperature,leaching time,nitric acid and dosage of phosphoric acid,were examined on recovery of tungsten.Results show that more than 97%of tungsten could be extracted under conditions of leaching temperature of 80-90°C,HNO3 concentration of 3.0-4.0 mol/L,liquild-to-soild ratio of 10:1,H3PO4 dosage of 3 stoichiometric ratio and leaching time of 3 h.Solvent extraction was then employed for the W recovery from the leachate with a organic system of 40%(v/v)N235,30%(v/v)TBP,and 30%sulfonated kerosene.Approximately 99.93%of W was extracted and ammonium tungstate solution containing 193 g/L W was obtained with a stripping rate of 98.10%under the optimized conditions.

Potentially fatal electrolyte imbalance caused by severe hydrofluoric acid burns combined with inhalation injury: A case report

BACKGROUND Hydrofluoric acid(HF)is one of the most common causes of chemical burns.HF burns can cause wounds that deepen and progress aggressively.As a result,HF burns are often severe even if they involve a small area of the skin.Published cases of HF burns have mostly reported small HF burn areas.Few cases of HF inhalation injury have been reported to date.CASE SUMMARY A 24-year-old man suffered from extensive hydrofluoric acid burns covering 60%of the total body surface area(TBSA),including deep second degree burns on 47%and third degree burns on 13%of the TBSA,after he fell into a pickling pool containing 15%HF.Comprehensive treatments were carried out after the patient was admitted.Ventricular fibrillation occurred 9 times within the first 2 h,and the lowest serum Ca2+concentration was 0.192 mmol/L.A dose of calcium gluconate(37 g)was intravenously supplied during the first 24 h,and the total amount of calcium gluconate supplementation was 343 g.Extracorporeal membrane oxygenation(ECMO)was applied for 8 d to handle the acute respiratory distress syndrome(ARDS)induced by the HF inhalation injury.The patient was discharged after 99 d of comprehensive treatment,including skin grafting.CONCLUSION Extensive HF burns combined with an inhalation injury led to a potentially fatal electrolyte imbalance and ARDS.Adequate and timely calcium supplementation and ECMO application were the keys to successful treatment of the patient.

Treatment of hydrofluoric acid exposure to the eye

AIM: To review the current evidence of the treatment of hydrofluoric acid(HF) exposure to the human cornea.METHODS: A comprehensive manual search of the literature was conducted through the Ovid interface to assess the mechanism and efficacy of each irrigator through a variety of clinical cases and experimental studies.· RESULTS: Ocular exposure to HF is extremely damaging to the eye and swift recognition and decontamination with an appropriate agent forms the basis of treatment. Although there are various decontamination solutions that have efficacy against the corrosive action of HF, irrigation with Hexafluorine proved to be the most safe and effective treatment for the eye.CONCLUSION: In conclusion emergency departments could benefit from the availability of Hexafluorine for the treatment of HF ocular burns in patients.

Leaching kinetics of acid-soluble Cr(Ⅵ) from chromite ore processing residue with hydrofluoric acid

Leaching kinetics of acid-soluble Cr（VI） in chromite ore processing residue （COPR） using hydrofluoric （HF） acid solution as a leaching agent was investigated for potential remediation of COPR with industrial waste water containing HF. The results show that HF can effectively destabilize the Cr（VI）-bearing minerals, resulting in the mobilization of Cr（VI） from COPR into the leachate. Particle size significantly influences the leaching of acid-soluble Cr（VI） from COPR, followed by leaching time, whereas the effects of HF concentration and leaching temperature are slight and the influence of stirring rate is negligible. The leaching process of acid-soluble Cr（VI） from COPR is controlled by the diffusion through the product layer. The apparent activation energy is 8.696 kJ/mol and the reaction orders with respect to HF concentration and particle size is 0.493 8 and -2.013 3, respectively.

Kinetic study on leaching of nickel from Turkish lateritic ore in nitric acid solution

Dissolution kinetics of nickel from lateritic ore in nitric acid solution was investigated. Experimental parameters used were stirring speed(100-600 r/min), temperature(40-96 °C), nitric acid concentration(0.1-2 mol/L) and particle size(<106 μm). The shrinking core model was applied to the results of experiments investigating the effects of leaching temperature in the range of 40-90 °C and nitric acid concentration in range of 0.1-2 mol/L on nickel dissolution rate. The kinetic analysis shows that the nickel dissolution from lateritic ore could be described by diffusion model. The activation energy(E_a) for the dissolution reaction is calculated as 79.52 kJ/mol.

Kinetics of nitric acid leaching of low-grade rare earth elements from phosphogypsum

Phosphogypsum(PG)is a potential resource for rare earth elements(REEs).Several studies have been carried out on REE leaching from PG.However,few in-depth studies have investigated the kinetics of this leaching process.In this study,the leaching kinetics of REEs from PG in nitric acid at different temperatures were explored in depth.The experiments show that the maximum leaching recovery for ΣREE was 58.5%,75.9%and 83.4%at 30,60 and 80℃,respectively.Additionally,among La,Ce,Y and Nd,Y had the highest leaching rate.A new shrinking core model(SCM)based on the dissolution reaction of a cylindrical solid particle with interfacial transfer and diffusion across the product layer as the rate-controlling step was deduced and could well fit the leaching process of REEs from PG.The activation energies for the leaching of La,Ce,Y and Nd were determined on the basis of the new cylindrical SCM.In summary,the cylindrical SCM was a more suitable fitting model than the spherical SCM,and the interfacial transfer and diffusion across the product layer were the rate-controlling step for REE leaching from the PG sample.

Extraction of cerium(Ⅳ) using tributyl phosphate impregnated resin from nitric acid medium

Tributyl phosphate （TBP） solvent was used for impregnation into Amberlite XAD-16 nonionic polymeric resin beads using the wet method to prepare solvent impregnated resin （SIR）. Undiluted TBP in a ratio to the resin support （volume to mass） of 6.0 at room temperature （RT） in 24 h was impregnated the resin with a mass ratio of 1.944, while the prepared gross sample of SIR at the ratio of solvent to resin of 3.0 was impregnated with a mass ratio of 1.88. Cerium（Ⅳ） oxide concentrate, prepared from crude Egyptian monazite sand, containing 37% cerium, 1.6% thorium and about 40% the other trivalent rare earth oxides, was used to prepare cerium（Ⅳ） nitrate solution for extraction using the prepared SIR. The impregnated resin was satisfactory for Ce（Ⅳ） extraction from nitric acid medium at room temperature. Cerium loading capacity of the impregnated resin reached 95.6% of the calculated theoretical capacity （173 g/kg （Ce/SIR）） under the conditions of 51.57 g/L cerium and 2.48 g/L thorium, 5.0 mol/L free nitric acid, solution to resin ratio of 10.0 and contacting the phases for 5.0 min. The loading capacity reached 98.75% when cerium concentration was increased to 91.43 g/L under the same conditions.

Exogenous Application of Salicylic Acid and Nitric Oxide on the Ionic Contents and Enzymatic Activities in NaCl-Stressed Soybean Plants

The possible protective role of exogenous SA and NO donor (sodium nitroprusside) against salt stress was examined NaCl-induced oxidative stress in Glycine max L. The results indicated that NaCl-induced ionic toxicity led to significant increase of Na+ uptake in root and shoot of soybean, while K+ and Ca2+ uptake was decreased markedly. Application of SA, SNP and the combination of SA with SNP inhibited Na+ uptake, but improved K+ and Ca2+ uptake. Under NaCl salinity, germination percentage (GP) was decreased significantly as compared with control plants. Moreover, the activity of lipoxygenase (LOX) was increased by NaCl, while the application of SA, NO and SA + SNP could decrease LOX activity in this condition. As well, activities of the polyphenol oxidase (PPO) and phenylalanine ammonia lyase (PAL) were significantly decreased by 100 mM NaCl, while the application of exogenous SA and NO increased the activities of PPO and PAL. In addition, it was observed that the SA and NO have effective functions in decreasing the damages induced by NaCl salinity. The seeds of G. max cv. Union × Elf (called L17) were obtained from the Institute of Sapling and Seed in Tehran and experiments have been done in Science and Research Branch, Islamic Azad University. After treatment with SA, SNP and NaCl, the plants were harvested for the estimation of ionic contents and assay of enzyme activities. The results showed that SA and NO act synergistically to reduce the damaging effects of salt tress via enhancing the activity of antioxidative systems.

Mechanism of oxidation of low rank coal by nitric acid

The pretreatment of low rank coal with nitric acid oxidation can promote its bio-liquefaction. However, the detailed mechanism of which remains an unresolved problem. In the present work, the characteristics of Fushun coal before and after oxidation by nitric acid were investigated combined with elemental composition, pore volume and pore size, Zeta potential, FT-IR, and 13C solid NMR spectrum analysis. The results show that the inorganic substance inlaid in coal are dissolved by ni- tric acid, which results in the decrease of coal ash content and increase of pore volume and pore size. Furthermore, there exist obvious chemical reactions between nitric acid and the functional groups of coal including aromatic ring carboxylation, side chain alkyl of aromatic ring oxidation and aromatic ring nitration. Among these reactions, some led to the increase in content of carboxyl, aliphatic carbon connected with O and humic acid carbon, while others caused the reduction of aromaticity, methyl carbon, substituted aryl carbon and side chain.

Chlorine inclusion mechanism in high purity copper electrorefining from nitric acid system

A practical approach was introduced to study the inclusion mechanism of chlorine in high purity copper electrorefining from nitric acid system via cyclic voltammetry(CV) combined with electrodeposition experiments. The CV curves display an obvious reduction peak of Cu Cl intermediate, which can provide an insight into the electrochemical behavior of this inclusion. Experimental results show that the increase of HNO3 concentration is favorable to reducing the quantity of chlorine inclusion although there is a slight decline in cathodic current efficiency. The optimum conditions for copper electrorefining in nitric acid system are HNO3 concentration in solution of 1-2 mol/L, moderate temperature of ~35 ℃ with current density not exceeding 25 m A/cm2. Based on the theoretical studies, an optimized copper electrorefining experiment was designed to simulate the industrial electrolysis, by which high purity copper can be obtained with chlorine inclusion less than 10 μg/g and current efficiency higher than 90%.

A Durable Catalyst for Vapor Phase Nitration of Benzene with Nitric Acid

Experimental results in this work demonstrate that PW12-H2SO4/SiO2 catalyst is a good and durable catalyst for vapor phase nitration of benzene to nitrobenzene (NB) using 65% nitric acid at normal pressure. It retains the advantages of using H2SO4 as catalyst and the addition of phosphotungstic acid holds back the effusion of sulfuric acid. This new catalyst keeps high activity (the conversion of HNO3 is more than 92%), high selectivity of NB (more than 97%) and high space time yield (STY 1.5 kg NB/kg cat.h) even after 150 h on stream, under condition of 423 K, SV=3200 ml/g h.

Corrosion behavior of porous Ti_3SiC_2 in nitric acid and aqua regia

Porous Ti3SiC2with high purity was synthesized using TiH2,Si and C powders with mole ratio of Ti to Si to C being3:1.2:2by reactive synthesis method.The corrosion behaviors of porous Ti3SiC2in nitric acid and aqua regia were investigated byimmersing test.Scanning electron microscope(SEM),X-ray diffractometer(XRD),energy dispersive spectrometer(EDS)and X-rayphotoelectron spectroscopy(XPS)were used to analyze the morphology,compositions and element contents of the samples beforeand after corrosion to determine the corrosion product and corrosion mechanism.The mass loss values of porous Ti3SiC2are26.9and132.5μg/cm2,respectively after immersing in nitric acid and aqua regia for600h.The results indicate that Ti3SiC2transforms toTi5Si3which has better corrosion resistance in nitric acid and aqua regia with mass loss values of9.34and7.06μg/cm2under thesame immersing time,respectively.The dramatic dissolution of porous Ti3SiC2in the acids is due to its special microstructure.

Solvent extraction equilibrium of dysprosium(Ⅲ) from nitric acid solutions with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester

In view of the importance of solvent extraction of rare earth metals with the acidic organophosphorous reagent,the development of a chemically based model applicable to high concentration is desired.In the present study,the equilibrium distribution of dysprosium(Ⅲ)between an aqueous nitric acid solution and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (PC88A)was measured in the range of an initial aqueous dysprosium(Ⅲ)concentration from 1.0×10-3to 1.0×10-1kmol/m 3and PC88A concentration from 0.16 to 0.65 kmol/m3in Shellsol D70 as the diluent.The obtained data were analyzed using the chemically based model in order to correlate the equilibrium distribution ratios.In this model,dysprosium(Ⅲ)was assumed to be extracted with the PC88A dimer as a 1:3 complex,the activities were considered for the aqueous species,and the effective concentration of the PC88A dimer was calculated using Alstad's empirical equation.As a result,the apparent extraction equilibrium constant was determined to be 253(kmol·m- 3)-2with an excellent correlation between the experiment and calculation results in the wide range of the logarithm of the distribution ratio from-2 to 3.5.In conclusion,the methodology in this model would be effective for quantitative description of solvent extraction behavior of general rare earth elements as well as dysprosium.

Extraction of lanthanide ions with N,N,N′,N′-tetrabutyl-3-oxadiglycolamide from nitric acid media

Extractability and extraction mechanism of lanthanide ions were investigated by using a new extractant,N,Nn,N′,N′-tetrabutyl-3-oxa-diglycolamide(TBDGA),in toluene from nitric acid media.The effects of HNO_3 and TBDGA concentrations,and temperature,on extraction of lanthanide ions were studied.Stoichiometrics of the main extracted species were HNO_3·TBDGA and M(NO_3)_3-3TBDGA(M = Er,Dy,Tb,Gd,La,Ce,Nd,Sm and Eu).The extracted species for metal ions were established to be ionic complex.In this complex,nitrate anion was not coordinated to the central ion.The extraction pattern increased gradually across the lanthanide ions series,showing enhanced affinity of TBDGA toward heavy lanthanide ions.Thermodynamic parameters were investigated for the exothermic extraction reaction.

Endogenous nitric oxide and hydrogen peroxide detection in indole-3-butyric acid-induced adventitious root formation in Camellia sinensis

Nitric oxide（NO）and hydrogen peroxide（H2O2）are essential signaling molecules with key roles in auxin induced adventitious root formation in many plants.However,whether they are the sole determinants for adventitious root formation is worth further study.In this study,endogenous NO and H2O2 were monitored in tea cutting with or without indole-3-butyric acid（IBA）treatment by using the fluorescent probes diaminofluorescein diacetate（DAF-2DA）and 2＇,7＇-dichlorodihydrofluorescein diacetate（DCF-DA）,respectively.The overproduction of NO and H2O2 was detected in the rooting parts of tea cuttings treated with or without IBA.But little NO and H2O2 was detected before the initiation phase of tea cuttings even with IBA treatment indicating that they might be not directly induced by IBA.Further carbon and nitrogen analysis found that the overproduction of NO and H2O2 were coincident with the consumption of soluble sugars and the assimilation of nitrogen.These results suggest that rooting phases should be taken into consideration with the hypothesis that auxin induces adventitious root formation via NO-and H2O2-dependent pathways and sink establishment might be a prerequisite for NO and H2O2 mediated adventitious root formation.