Nitric Acid Solution Research Articles

Environmentally friendly solvent debinding technique of POM binder system for titanium injection molding

An environment-friendly solvent debinding process for polyoxymethylene (POM) for metal injection molding (MIM) is presented as an alternative to the traditional catalytic debinding method. This study investigated the influence of various acid solvents and debinding temperature. The optimal debinding parameters were 5 M nitric acid solution at 60 °C. Based on the calculation of effective diffusivity and activation energy, the solvent-debinding mechanism for POM is proposed. The removal of POM was controlled by three processes: dissolution, diffusion, and chemical reaction. The resulting final titanium parts have a high density of over 95% and an ultimate tensile strength of 406 MPa.

The distribution coefficients of Nd3+ and Y3+ between 0.1 and 2.1 M HNO3 and HDEHP at 298.15 K

Rare earth metals are considered to be some of the most critical raw materials on the planet due to their use in many products and technologies, the difficulty in isolating the individual elements from ores and each other, and the market restrictions that threaten their supply. However, despite this, the recycling rates for rare earth metals remain low. Hydrometallurgy has been proposed to hold the greatest potential for the recovery of rare earth metals from waste materials. However, the design of hydrometallurgical processes for the recovery of rare earth elements from waste requires a good understanding of the behaviour of the rare earth metals between different phases.In this study, the distribution coefficients of two rare earth metals, yttrium, and neodymium, between an organic solvent; bis(2-ethylhexyl) phosphate, diluted in n-dodecane at between 0.25 M and 1 M; and an aqueous nitric acid solution at concentrations of between 0.1 M and 2.8 M were measured. Distribution measurements were performed using a series of liquid–liquid extraction cells at a constant temperature of 298.2 K. The concentration of the rare earth metals was measured using ICP-OES analysis. The distribution coefficients and the acid concentration were found to be inversely related to each other. Conversely, the distribution coefficients were directly proportional to the concentration of the solvent in the organic phase.The data reported in this paper will be used to design a counter-current liquid–liquid extraction column for the recovery of neodymium from waste permanent magnet powder.

Next-Generation 3,3'-AlkoxyBTPs as Complexants for Minor Actinide Separation from Lanthanides: A Comprehensive Separations, Spectroscopic, and DFT Study.

Progress toward the closure of the nuclear fuel cycle can be achieved if satisfactory separation strategies for the chemoselective speciation of the trivalent actinides from the lanthanides are realized in a nonproliferative manner. Since Kolarik's initial report on the utility of bis-1,2,4-triazinyl-2,6-pyridines (BTPs) in 1999, a perfect complexant-based, liquid-liquid separation system has yet to be realized. In this report, a comprehensive performance assessment for the separation of 241Am3+ from 154Eu3+ as a model system for spent nuclear fuel using hydrocarbon-actuated alkoxy-BTP complexants is described. These newly discovered complexants realize gains that contemporary aryl-substituted BTPs have yet to achieve, specifically: long-term stability in highly concentrated nitric acid solutions relevant to the low pH of unprocessed spent nuclear fuel, high DAm over DEu in the economical, nonpolar diluent Exxal-8, and the demonstrated capacity to complete the separation cycle with high efficiency by depositing the chelated An3+ to the aqueous layer via decomplexation of the metal-ligand complex. These soft-N-donor BTPs are hypothesized to function as bipolar complexants, effectively traversing the organic/aqueous interface for effective chelation and bound metal/ligand complex solubility. Complexant design, separation assays, spectroscopic analysis, single-crystal X-ray crystallographic data, and DFT calculations are reported.

Efficient separation of radium from natural thorium using a mesoporous silica-supported composite resin with sulfonic acid groups for the acquisition of targeted α-nuclides 212Pb

212Pb serves as one of the most important nuclides for targeted alpha therapy (TAT), with good potential in the treatment of malignant tumors. However, medical and clinical applications are seriously limited by its extremely short supply, which strongly depends on the acquisition of its parent nuclides such as 228Ra or 224Ra. To address this issue, we conducted a systematic investigation on the separation of trace radium from natural thorium using the ion exchange chromatography method, and a novel porous silica-based composite resin functionalized with sulfonic acid groups was prepared, characterized, and employed. Experimental results showed that the silica-supported resin was successfully prepared with the sulfonic acid groups, and possessed small particle size, mesoporous pore structure and large specific surface area. The resin exhibited high selectivity toward thorium compared with barium, and the separation factor reached 123 at low acidity and at low temperature. The resin demonstrated a fast adsorption speed and an excellent separation performance, and the adsorption mechanism was confirmed based on the ion exchange between the sodium carried and the target cations. On the basis, column experiments were further conducted and finally the separation of trace radium from thorium was realized using a small column filled with about 1.0 g resin. The chemical recovery of radium reached 97 %, and the decontamination factor for thorium exceeded 40,000. This work verifies the feasibility of directly extracting 228Ra and 224Ra from natural thorium using the sulfonic acid group functionalized materials in the dilute nitric acid solution, and presents an excellent material and systematic experimental data on the separation activities, rendering this study particularly significant.

Pilot-scale Validation of the Modeling of NOx Reactive Absorption Process Using Aqueous Solutions Containing Nitric Acid and Hydrogen Peroxide

NOx are harmful pollutants emitted by many industries and must be removed before the gases are released into the atmosphere. Among the various techniques used for NOx removal, reactive absorption by hydrogen peroxide in a packed column has the advantage of being able to transform NOx into nitric acid which can be recycled and reused in the plants. This work aimed at modeling the NOx absorption by means of aqueous solutions of hydrogen peroxide and nitric acid, applied in a packed column operating under different representative conditions. The model established using the Aspen software considers the equilibrium and the kinetics of the reactions taking place both in the gas phase and in the liquid phase as well as the thermodynamic properties of the chemical (molecular and ionic) components estimated using the Electrolyte NRTL model. It allows predicting NOx absorption performances in terms of efficiency and selectivity. The model was validated by comparing simulation results with experimental ones obtained in a pilot-scale absorption column and published previously. The predicted values are in satisfactory agreement with the experimental data showing a deviation between 5 and 8%. Therefore, the model developed in this work could be advantageously used to design industrial-scale reactive NOx absorption columns.

Effect of alkali metal nitrates on palladium dissolution in nitric acid solutions

Hydrometallurgical unit operations are typically used to recover palladium (Pd) from its ores and secondary resources with high selectivity owing to their low energy consumption, cost effectiveness, and volume flexibility. Herein, diluted HNO3 solutions with added nitrate salts were used to dissolve Pd powders. Moreover, solutions of nitrates with same valency cations (such as HNO3, LiNO3, NaNO3, KNO3, CsNO3, and NH4NO3) and same period cations (such as NaNO3, Mg(NO3)2, and Al(NO3)3) were used to reveal the involved beneficial effects of the nitrates on the Pd dissolution in an environment friendly way with low acidity of the solutions. Among all added alkali metal nitrates, LiNO3 resulted in the highest Pd dissolution efficiency, which was attributed to the higher dissociation constant of LiNO3, resulting in a higher concentration of free nitrate and hence a higher oxidation potential of the overall system. The dissolution process was systematically investigated to determine the optimal temperature (353 K), LiNO3 and HNO3 concentrations (6 and 1 mol L−1, respectively), stirring speed (500 rpm), and reaction time (5 h). These optimal conditions yielded a dissolution efficiency of 99.6%. Notably, as the reaction proceeded, the Pd powder surfaces corroded to form numerous holes, indicating that internal diffusion control also affected Pd dissolution.

Multistage hydrometallurgical process for enhanced recovery and individual separation of Nd and Pr from NdFeB magnet scrap

This study introduces a multistage hydrometallurgical process designed for the recovery and individual separation of Nd and Pr from NdFeB magnet scrap. Following demagnetization, the magnet underwent crushing, grinding, and leaching using a sulfuric acid solution. The pH of the resultant leachate was subsequently adjusted to 1.2 using a NaOH solution, leading to the precipitation of Nd and Pr as sodium double sulfates. The produced double sulfate was then mixed with a saturated NaOH solution, resulting in the formation of rare earth hydroxide. The hydroxide was further decomposed into oxides (REO) after calcination at 500°C. The REO was dissolved in hydrochloric acid and nitric acid solutions to investigate the individual separation of Nd and Pr using the D2EHPA–TOA extractant system and compare the results with D2EHPA-only system. It was concluded that the extraction mechanism of D2EHPA–TOA system is highly dependent on the acidity of the solution, with TOA having a synergistic effect on the REE extraction when pH > 3, and an antagonistic effect when pH ≤ 3. In terms of extraction efficiency, both extractant systems demonstrated efficiency levels exceeding 99% when the pH was ≥2, with similar behavior when extraction was performed in HCl and HNO3 media. Although both extractant systems yielded unsatisfactory outcomes in the separation of Nd and Pr, a marginal improvement was observed with the incorporation of TOA into the extractant system. This observation implies the potential of exploring analogous combinations in future studies.

Acid Treatments of Ti-Based Metallic Glasses for Improving Corrosion Resistance in Implant Applications

Ti-based bulk metallic glasses are promising materials for metallic bone implants, mainly due to their mechanical biofunctionality. A major drawback is their limited corrosion resistance, with high sensitivity to pitting. Thus, effective surface treatments for these alloys must be developed. This work investigates the electrochemical treatment feasibility of nitric acid (HNO3) solution for two bulk glass-forming alloys. The surface states obtained at different anodic potentials are characterized with electron microscopy and Auger electron spectroscopy. The corrosion behavior of the treated glassy alloys is analyzed via comparison to non-treated states in phosphate-buffered saline solution (PBS) at 37 °C. For the glassy Ti47Zr7.5Cu38Fe2.5Sn2Si1Ag2 alloy, the pre-treatment causes pseudo-dealloying, with a transformation from naturally passivated surfaces to Ti- and Zr-oxide nanoporous layers and Cu-species removal from the near-surface regions. This results in effective suppression of chloride-induced pitting in PBS. The glassy Ti40Zr10Cu34Pd14Sn2 alloy shows lower free corrosion activity in HNO3 and PBS due to Pd stabilizing its strong passivity. However, this alloy undergoes pitting under anodic conditions. Surface pre-treatment results in Cu depletion but causes enrichment of Pd species and non-homogeneous surface oxidation. Therefore, for this glassy alloy, pitting cannot be completely inhibited in PBS. Concluding, anodic treatments in HNO3 are more suitable for Pd-free glassy Ti-based alloys.

High surface area microporous carbon nanocubes from controlled processing of graphene oxide nanoribbons

A new, facile, and template-free method to prepare high surface area microporous carbon nanocubes (CNCs) from a mixture of graphene oxide nanoribbons (NRs), graphene oxide, and carbon dots is reported. The nanoribbons, approximately 30 nm wide and with lengths ranging from a few tens of nanometres up to several micrometres, were obtained from the oxidation of Black Pearls 2000 carbon black in nitric acid solution. The non-purified nanoribbons further contained additional fragments of graphene oxide, and of graphene oxide quantum dots. Slow pyrolysis of the nanoribbon mixture with slow heating rates, e.g., 3 °C/min, yielded carbon nanocubes approximately 250 nm in size with surface areas greater than 900 m2/g. Heating rates of 50 °C/min led to carbons with ∼800 m2/g surface area but bulk morphology. Precipitating the nanoribbons in potassium hydroxide solution, followed by carbonization, yielded microporous nanoparticle aggregates that were 20 nm in size with surface areas greater than 2000 m2/g. The particles exhibited complex, quasi-spherical morphology. Pyrolysis of other products obtained from oxidation in HNO3 of different grades of carbon black, specifically graphene oxide nanoparticles and quantum dots, yielded high surface area microporous carbons but with bulk morphology regardless of the processing conditions. Despite the lower surface area and pore volume of the CNCs in comparison to the nanospheres, the former contained ultramicropores that were highly accessible to CO2 as a molecular probe and had excellent selectivity of CO2 over N2. Hence, CNC materials have promising properties for applications where particle surface-to-volume ratios, high internal surface areas, and abundant super and ultramicropores are desired.

Two-stage leaching of calcium and vanadium from high-calcium steelmaking slag

ABSTRACT Vanadium (V) is a critically important element in many industries. A widely used recovery process is a combination of roasting and leaching. However, roasting is an energy-intensive stage. Generally, basic oxygen furnace (BOF) slag is high in calcium (Ca) but low in V. Ca content and its chemical nature can prevent V leaching. This study presents a potential two-stage leaching process for Ca and V from BOF slag. The method is environmentally friendly using low temperatures and enabling leachate recycling. Furthermore, the utilisation rate of the slag can be higher due to Ca recovery. Ca is first leached using ammonium nitrate and nitric acid solution. The V-containing residue is directed to the second stage, where V is leached using ammonium carbonate ((NH4)2CO3). Ca leaching efficiency was 71% achieved with a low temperature (40°C) and in 20 min. > 99% of the dissolved element was Ca. Increasing the total nitrate concentration increased the leaching efficiency. Reducing the L/S ratio improved selectivity. The solid material was analysed after the leaching stages and a clear change was observed after the Ca-stage. The V leaching efficiency was 50%. > 88% of dissolved element was V (L/S 8, [(NH4)2CO3] 200 g/L, 60°C, and 60 min). Increasing [(NH4)2CO3] and L/S ratio slightly improved the leaching efficiency but decreased selectivity. The studied process implements circular economy principles and has been developed for side streams with low V concentrations. However, further optimisation and developments are required regarding the effectiveness of the process.

Efficient Topical Treatment of Canine Nodular Sebaceous Hyperplasia with a Nitric Acid and Zinc Complex Solution.

Nodular sebaceous gland hyperplasia in the often middle-aged to old dog is a common, benign proliferation that results in exophytic, pink to yellow, alopecic, and often multilobulated nodules. Removal is usually carried out by surgical excision. As many old dogs have comorbidities that increase the risk of anesthesia, a topical treatment is warranted. We hypothesized that the application of a solution containing nitric acid, zinc, copper, and organic acids (Verrutop®), would be a safe and efficient way to treat these nodules. Eleven dogs with a total of 29 nodules, grossly compatible with nodular sebaceous gland hyperplasia, were included in the study. Eighteen of the nodules were treated; 11 were left untreated. No anesthesia or sedation was needed. Four weeks after one application, 17/18 treated nodules had decreased by 100% in volume. There was a statistically significant difference in percentual volume change between the treated and untreated nodules from day 0 to day 28 (p < 0.0001). No serious side effects were noted. Sebaceous hyperplasia cannot always be distinguished grossly from sebaceous tumors. Cytological evaluation can be helpful, and in cases of deviant macroscopic features, local recurrence, or more aggressive behavior, the appropriate intervention would be to biopsy or excise the nodule for histopathology. Topical application of Verrutop® is an easy, low-cost, and efficient way to remove canine sebaceous gland hyperplasia with minimal side effects in cases where surgery and anesthesia are not desired.

Investigation of the inlet useful temperature difference effect on the distribution of hydrodynamic characteristics of the vapor-liquid flow inside the falling-film evaporator heating tube designed for a nitric acid solutions evaporation

We present the results of mathematical modeling of effect of inlet useful temperature difference on the vapor- liquid flow in the heat exchange tube of a vertical evaporating film apparatus, which is designed for evaporation of nitric acid solutions. Distributions obtained along the heat exchange tube length of local values of the: mass flow rate of the fluid and secondary steam, the velocity of the fluid film, the velocity of the secondary steam, the Reynolds criterion of the liquid and vapor phases, the absolute pressure depending on the values of this useful temperature difference. The study was carried out using numerical simulation. To study the effect of the initial useful temperature difference on the hydrodynamics of the vapor-liquid flow, the vertical evaporator equipped with the tube ø38x3 mm and length of L = 4 m was adopted. The linear nature of the distribution of hydrodynamic parameters along the length of the heat exchange tube is established. The absolute pressure in the tube space decreases along the heating tube due to pressure drop. The limiting factor in reducing the absolute pressure is the friction losses of the secondary vapor on the solution film surface. A decrease in the pressure in the tube space leads to decrease in the boiling point of the solution. This leads to increase useful temperature. This has a positive effect on the evaporation efficiency The obtained data should be used in the design of evaporation plants, which are designed for evaporation of nitric acid solutions.

Synthesis, characterization and optimization of sulfonated poly-ether-ether-ketone (sPEEK)/functionalized carbon nanotubes (c-CNTs) nanocomposite membranes for fuel cell application

Poly-ether ketone (PEEK) was modified to sulfonated poly-ether ketone (sPEEK) by sulfonation process with a degree of sulfonation 49.5%. Carbon nanotubes were acid-treated with sulfuric acid and nitric acid solution (3:1, v/v) for functionalization. sPEEK and sPEEK/c-CNT membranes were prepared by solvent casting method using dimethyl sulfoxide (DMSO) as solvent. The experimental part was conducted as per design of experiment employing response surface methodology consisting of three factors, namely (A) c-CNT (wt.%), (B) mixing temperature (°C), and (C) sPEEK concentration (mg/mL). The ion exchange capacity was found to increase with c-CNT (wt.%). Fourier-transform infrared spectroscopy confirms the sulfonation of PEEK. X-Ray diffraction investigates the influence of the sulfonation in the crystal structure of the sPEEK and sPEEK/c-CNT. Scanning electron microscopy images show that c-CNTs are dispersed well in the sPEEK matrix. The results showed slightly increasing water uptake and swelling ratio of the composites membranes. The analysis of variance (ANOVA) revealed that c-CNT (wt.%) is highly affecting the responses. Proton conductivity of sPEEK specimen is about 23.9 mS/cm, which is significantly increased to 57.0 mS/cm for sPEEK/0.12 c-CNT (wt.%) membrane suggesting its application for fuel cell.

Sorption Treatment of Nitric Acid Solutions to Remove Tributyl Phosphate and Hexachlorobutadiene

Sorption Treatment of Nitric Acid Solutions to Remove Tributyl Phosphate and Hexachlorobutadiene

Effect of Irradiation on the Thermal Stability of Nitric Acid Solutions of Carbohydrazide

Effect of Irradiation on the Thermal Stability of Nitric Acid Solutions of Carbohydrazide

In-Depth Understanding of the Chemical Stripping Mechanism of AlSiY Coatings on Nickel Superalloys by First-Principles Calculation

In order to repair a failed AlSiY coating on aeroengine turbine components, the AlSiY coating was stripped using a nitric acid-based removal reagent. The homogeneity of chemical stripping was evaluated and the stripping mechanism was clarified using first-principles calculations. The effects of hydrofluoric acid (HF) and chromium trioxide (CrO3) on the homogeneity of chemical stripping were investigated by calculating the electronic work functions (EWFs) of the stripped surfaces. The results showed that the stripped surfaces of the AlSiY coating exhibited a serrated appearance when it was etched by a single nitric acid solution, indicating severely inhomogeneous stripping. With the addition of HF and/or CrO3, the homogeneity of chemical stripping could be greatly improved, which was attributed to the increased EWF of the (200) surface and the decreased EWF of the (110) surface, causing the corrosion cathode to transition from the (110) surface to the (200) surface. The HF+CrO3+HNO3 mixed reagent was the optimal combination for the uniform stripping of the AlSiY coating, while the inner layer was not broken. The Al atoms on the surface could be preferentially removed due to the strong bonding with acid ions. The research method proposed in the present work will provide a new means to design chemical removal reagents.

Estimating the corrosion rate of stainless steel R-SUS304ULC in nitric acid media under concentrating operation

The amount of corrosion of the austenitic stainless steel was evaluated considering the changes in solution composition and boiling during actual concentration operations. Austenitic stainless steel R-SUS304ULC is the structural material of the highly radioactive liquid waste concentrator in Japanese spent fuel reprocessing plant, which treats highly corrosive nitric acid solutions during enrichment operations. The study results show that it is necessary to focus on nitric acid concentrations, oxidizing metal ion concentrations, and decompression boiling as factors that accelerate the corrosion rate of stainless steel because of cathodic reaction activation.

Extraction of Lithium and Synthesis of Kaolinite from α‐Spodumene via Alkali Calcination

AbstractExtracting lithium from spodumene by sulfuric acid roasting is the largest commercialized way at present, which not only consumes a large amount of energy but also produces massive waste residue that will cause environmental problems. In this work, a new process for extracting lithium by directly decomposing α‐spodumene through alkali calcination is designed. The reaction of α‐spodumene with Na2CO3 at 750 °C for 2 h can decompose it and form nepheline and lithium silicate/sodium silicate. The nepheline and soluble lithium silicate/sodium silicate are separated by water leaching, and 93.9 % of lithium can be leached under optimal conditions. In addition, the synthesis of nano‐kaolinite is investigated with nitric acid solutions. Conversions of 98.7 % were obtained with 0.4 M nitric acid at 250 °C and an L/S ratio of 17.5 L/kg. The water leachate can precipitate Li2CO3 with a purity of 99.0 % by CO2 after desilicated by CaO. The final yields of Li2CO3 and kaolinite relative to the Li and Si content of the starting minerals are 91.4 % and 48.5 %, respectively. This new method achieves the full utilization of spodumene with lower energy consumption and demonstrates great potential for industrial applications.

THERMODYNAMICS OF STEPWISE DISSOCIATION OF GLYCYL-D-PHENYLALANINE IN AQUEOUS SOLUTION

Recently, more and more drugs that are derivatives of oligopeptides have been introduced to the pharmaceutical market. The structural elements of these compounds are amino acids and dipeptides. When stabilizing functional groups are introduced into the peptide structure, as well as through the use of special delivery systems, oligopeptide derivatives can be used as innovative medicines. The calorimetric method was used to determine the heat of interaction of glycyl-D-phenylalanine with solutions of nitric acid and potassium hydroxide at 298.15K and the values of the ionic strength of the solution 0.5, 0.75 and 1.0 in the presence of KNO3. Measurements were carried out on a calorimeter with an isothermal shell and automatic recording of the temperature-time curve. The unit was equipped with a reaction vessel with a volume of 60 cm3. Calibration was performed by current at T = (293.15–308.15) ± 0.01 K and P = 100.5± 0.7 kPa. A thermistor KMT-14 was used as a temperature sensor. The temperature of the calorimetric cell was controlled in a thermostat equipped with a PID controller with an accuracy of 0.002 K. The temperature sensor of the thermostat was a platinum resistance thermometer. The calorimeter was calibrated by current. The volume of the calorimetric liquid is 42.83 ml. The enthalpy of stepwise dissociation of glycyl-D-phenylalanine at zero ionic strength was found by an equation with one individual parameter. Standard thermodynamic characteristics (ΔrH°, ΔrG°, ΔrS°) of acid-base interaction reactions in aqueous solutions of glycyl-D-phenylalanine are calculated. The effect of the background electrolyte concentration on the dissociation heats of glycyl-D-phenylalanine is considered. Knowledge of the thermochemical characteristics of dipeptides is necessary for understanding and subsequent modeling of the process of protein biosynthesis occurring in biological systems. Data on the thermodynamic characteristics of dipeptide solutions are needed in various fields where these compounds are used: pharmacology, medicine, food and cosmetic industries, for the development, justification and optimization of technological processes involving these compounds and their complexes with metals.

Carbon materials for effective purification of aqueous solutions from tributyl phosphate.

This study investigates various sorbents for the effective sorption of dissolved organic substances, using tributyl phosphate (TBP) as a model compound. TBP is one of the most commonly used extractants in the nuclear industry. Four different carbon materials with high specific surface areas (2000-3000 m2 g-1) were selected for evaluation. The sorption of TBP from nitric acid solutions was examined over a wide range of concentrations. The samples with the largest specific surface areas showed the highest sorption capacity for organic matter. To enable repeated use, a purification scheme was developed to restore the sorbents' original properties. The samples were subjected to various treatments, analyzed using X-ray photoelectron spectroscopy, and used in subsequent sorption experiments.