This study investigated the process of reclaiming Mo from calcined waste hydrotreating (CWHT) catalysts using tributyl phosphate (TBP) as an extractant with electron-withdrawing properties. Using inductively coupled plasma (ICP) technology, the optimal operating conditions for Mo recovery were determined based on the metal ion content in different processes. Considering the pH impact on metal species in solution, an acid leaching solution with 6 M sulfuric acid was employed. After 3 h of reaction, 94 wt% of the Mo was transferred from the WHT catalyst to the acid leaching solution. Adjusting the filtrate to a pH of 1.5 allowed the TBP to selectively extract over 98.8 wt% of Mo from the aqueous filter solution into the organic phase. MC-Cabe-Thiele theory predicts that a three-stage countercurrent extraction can reduce Mo to less than 0.2 wt%. Stripping moved approximately 98 wt% of the Mo from the organic to the inorganic phases. The recovered colorless organic tributyl phosphate can be used in the recycled extraction process.
We prepared porous poly(ε-caprolactone)/poly(lactic-co-glycolic acid) (PCL/PLGA) 3D scaffolds with surfaces that were modified through the co-precipitation of calcium phosphate (CAP) with binary drug components, including risedronate (RSD) and hyaluronic acid (HyA). The 3D porous biodegradable PCL/PLGA scaffolds were fabricated by sintering microspheres prepared with a 30/70 PCL/PLGA blend. The co-precipitation of the CAP coating with binary drug components significantly enhanced the proliferation and differentiation of rat mesenchymal stem cells (rMSCs) on the scaffolds. Although the presence of both HyA and RSD positively improved proliferation and differentiation, HyA and RSD were more effective on osteoblastic proliferation and differentiation, respectively. These results strongly demonstrate that the drug effects on osteoblastic responses were closely interconnected. The two drugs affect rMSCs behavior in a concentration-dependent manner, requiring a balance between proliferation and differentiation for optimal bone regeneration. We expect this surface modification technique could potentially be utilized for the fabrication of functionalized biodegradable scaffolds and delivery of drug mixtures.
In this paper, the commercial anion exchange resin (IRA900) was used to investigate the adsorption properties, comparing the anion selectivity of phosphate and sulfate in water. The phosphate removal efficiency was 29.6% less than sulfate in single condition, and significantly decreased from 44.8% to 3.47 in mixed conditions while sulfate removal efficiency remained unchanged, confirming a higher selectivity for sulfate over phosphate. In the pH effect, phosphate removal efficiency increased with increase of pH due to the increased HPO4 2- species. The total removal efficiency of phosphate and sulfate was obtained approximately 62% in mixed condition, regardless of solution pH, indicating that the total anion exchange capacity was not influenced in the pH. The values of qmL and bL derived from Langmuir isotherm equation were 11.5 and 8.10 times higher for sulfate than for phosphate in mixed conditions. In single condition, sulfate and phosphate reached to equilibrium at 6 and 3 h, respectively. In mixed condition, phosphate was desorbed by the sulfate after 1h and the time to equilibrium for sulfate was retarded to 6h. Furthermore, when comparing the separation factor (αP/S), increasing the initial concentration led to higher selectivity of phosphate.
In this study, ferric phosphate precursors were prepared by controlling precipitation time, and the resulting LiFe PO4 active materials were thoroughly investigated. Microscale LiFePO4 cathode materials, designed for high energy density at the cell level, were successfully synthesized through a 10 h co-precipitation. As the reaction time increased, smaller primary particles were aggregated more tightly, and the secondary particles exhibited a more spherical shape. Meanwhile, ammonia did not work effectively as a complexing agent. The carbon coated LiFePO4 (LiFePO4/C) synthesized from the 10 h ferric phosphate precursor exhibited larger primary and secondary particle sizes, a lower specific surface area, and higher crystallinity due to the sintering of the primary particles. Enhanced battery performance was achieved with the LiFePO4/C that was synthesized from the precursor with the smaller size, which exhibited the discharge capacity of 132.25 mAh ‧ g-1 at 0.1 C, 70 % capacity retention at 5 C compared with 0.1 C, and 99.9 % capacity retention after the 50th cycle. The better battery performance is attributed to the lower charge transfer resistance and higher ionic conductivity, resulting from smaller primary particle sizes and a shorter Li+ diffusion path.
Building step-scheme (S-scheme) heterojunctions has recently emerged as a highly effective approach for developing superior photocatalysts for water purification. Herein, a C3N5/ Ag3PO4 (CA) S-scheme heterojunction was prepared by in situ growth of Ag3PO4 nanoparticles on 2D C3N5 nanosheets. Notably, under visible-light irridiation, CA exhibited significantly higher activity in the photodegradation of LEVO, which is about 28.38, 2.41, and 2.14 times higher than the rates for C3N5, Ag3PO4, and the mixture, respectively. Based on the radical scavenging experiments, the mechanism for enhanced photocatalytic performance has been analyzed, is attributed to improved interfacial charge separation, the elevated redox potential of photon-generated electrons and holes, and the increased generation of active species resulting from the S-scheme transfer of photoinduced carriers. Additionally, CA demonstrates greater stability than either C3N5 or Ag3PO4 alone in the photo-oxidation of LEVO and the photodegradation of RhB. In essence, this study not only deepens our comprehension of the photocatalytic mechanism of CA, but also pioneers a novel concept for the development of highly effective and stable S-type heterojunction photocatalysts.
The separation of zirconium and hafnium using tributyl phosphate (TBP)-Dodecane extractants in nitric acid medium was performed. Zirconium oxychloride, used as extraction feed, was obtained from the synthesis of Kalimantan zircon sand concentrate smelted using NaOH. The extraction process was carried out by dissolving chloride-based metals in nitric acid media in the presence of sodium nitrate using TBP-Dodecane as an extractant. Some of the extraction parameters carried out in this study include variations in organic phase and aqueous phase (O/A), variations in contact time, and variations in nitric acid concentration. Extraction was carried out using a mechanical shaker according to the parameter conditions. X-ray fluorescence (XRF) was used for elemental (Zr and Hf) composition analysis of the aqueous solution. The results showed that zirconium was separated from hafnium at optimum conditions with an organic/aqueous ratio of 1:5, contact time of 75 min, and an HNO3 concentration of 7 M. The resulting separation factor of zirconium and hafnium using TBP-Dodecane was 14.4887.
In response to the growing demand for high-performance lithium-ion batteries, this study investigates the crucial role of different carbon sources in enhancing the electrochemical performance of lithium iron phosphate ( LiFePO4) cathode materials. Lithium iron phosphate ( LiFePO4) suffers from drawbacks, such as low electronic conductivity and low lithium-ion diffusion coefficient, which hinder its industrial development. Carbon is a common surface coating material for LiFePO4, and the source, coating method, coating amount, and incorporation method of carbon have a significant impact on the performance of LiFePO4 materials. In this work, iron phosphate was used as the iron and phosphorus source, and lithium carbonate was used as the lithium source. Glucose, phenolic resin, ascorbic acid, and starch were employed as carbon sources. Ethanol was utilized as a dispersing agent, and ball milling was employed to obtain the LiFePO4 precursor. Carbon-coated LiFePO4 cathode materials were synthesized using the carbothermal reduction method, and the effects of different carbon sources on the structure and electrochemical performance of LiFePO4 materials were systematically investigated. The results showed that, compared to other carbon sources, LiFePO4 prepared with glucose as the carbon source not only had a higher discharge specific capacity but also better rate cycle performance. Within a voltage range of 2.5–4.2 V, the initial discharge specific capacities at 0.1, 0.5, and 1 C rates were 154.6, 145.6, and 137.6 mAh/g, respectively. After 20 cycles at a 1 C rate, the capacity retention rate was 98.7%, demonstrating excellent electrochemical performance.
The binary oxide adsorbent using Fe and Mn (Fe-Mn) has been prepared by precipitation method to enhance the removal of phosphate. Different amounts of chitosan, a natural organic polymer, were used during preparation of Fe-Mn as a stabilizer to protect an aggregation of Fe-Mn particles. The optimal amount of chitosan has been determined considering the separation of the Fe-Mn particles by gravity from solution and highest removal efficiency of phosphate (Fe-Mn10). The application of Fe-Mn10 increased removal efficiency at least 15% compared to bare Fe-Mn. According to the Langmuir isotherm model, the maximum uptake (qm) and affinity coefficient (b) were calculated to be 184 and 240 mg/g, and 4.28 and 7.30 L/mg for Fe-Mn and Fe-Mn10, respectively, indicating 30% and 70% increase. The effect of pH showed that the removal efficiency of phosphate was decrease with increase of pH regardless of type of adsorbent. The enhanced removal efficiency for Fe-Mn10 was maintained in entire range of pH. In the kinetics, both adsorbents obtained 70% removal efficiency within 5 min and 90% removal efficiency was achieved at 1 h. Pseudo second order (PSO) kinetic model showed higher correlation of determination (R2), suggesting chemisorption was the primary phosphate adsorption for both Fe-Mn and Fe-Mn10.
Bis (2-ethylhexyl)phosphoric acid (HDEHP) is a renowned extractant, favored for its affinity to selectively remove uranium via its P=O groups. We previously synthesized HDEHP-functionalized mesoporous silica microspheres for solid-phase uranium adsorption. Herein, we investigated the kinetic and isothermal behavior of uranyl ion adsorption in mesoporous silica microspheres functionalized with phosphate groups. Adsorption experiments were conducted by equilibrating 20 mg of silica samples with 50 mL of uranium solutions, with concentrations ranging from 10 to 100 mgU L−1 for isotherms and 100 mgU L−1 for kinetics. Three distinct samples were prepared with varying HDEHP to TEOS molar ratios (x = 0.16 and 0.24) and underwent hydrothermal treatment at different temperatures, resulting in distinct textural properties. Contact times spanned from 1 to 120 hours. For x = 0.16 samples, it took around 50 and 11 hours to reach equilibrium for the hydrothermally treated samples at 343 K and 373 K, respectively. Adsorbed quantities were similar (99 and 101 mg g-1, respectively), indicating consistent functional group content. This suggests that the key factor influencing uranium adsorption kinetics is pore size of the silica. The sample treated at 373 K, with a larger pore size (22.7 nm) compared to 343 K (11.5 nm), experienced less steric hindrance, allowing uranium species to diffuse more easily through the mesopores. The data confirmed the excellent fit of pseudo-second-order kinetic model (R2 > 0.999) and closely matched the experimental value, suggesting that chemisorption governs the rate-controlling step. To gain further insights into uranium adsorption behavior, we conducted an adsorption isotherm analysis at various initial concentrations under a constant pH of 4. Both the Langmuir and Freundlich isotherm models were applied, with the Langmuir model providing a superior fit. The relatively high R2 value indicated its effectiveness in describing the adsorption process, suggesting homogenous sorbate adsorption on an energetically uniform adsorbent surface via a monolayer adsorption and constant adsorption site density, without any interaction between adsorbates on adjacent sites. Remarkably, differences in surface area did not significantly impact uranium removal efficiency. This observation strongly suggests that the adsorption capacity is primarily governed by the loading amount of HDEHP and the inner-sphere complexation with the phosphoryl group (O=P). Our silica composite exhibited an impressive adsorption capacity of 133 mg g-1, surpassing the results reported in the majority of other silica literature.
In KAERI’s previous phosphate precipitation tests, the dispersed powder of lithium phosphate (Li3PO4) as a precipitation agent reacted with various metal chlorides in a simulated LiCl-KCl molten salt. The reaction of metal chlorides composed of actinides such as uranium and three rare earths (Nd, Ce and La) with lithium phosphate is a solid-liquid reaction. A phosphorylation reaction rate is very fast and the metal phosphates as a reaction product precipitated on the bottom of the molten salt crucible. One of the recovery methods of the metal phosphate precipitates is segregation the lower part (precipitates) of the salt ingot using the various cutting tools. Recently, a new phosphorylation experiment using lithium phosphate ingots carried out in order to collect the metal phosphate precipitates into a small recovering vessel, and the test result of this new method was feasible. However, the reaction rate of test using lithium phosphate ingot is extremely slower than that of test using lithium phosphate powder. In this study, the precipitation reactor design (a tapered crucible with polished inner surface) used for phosphorylation reaction showed that the salt ingot with metal phosphate precipitates could be detached from a tapered stainless steel crucible. We propose that the recovery of precipitates from a salt ingot is possible by introducing a dividing plate structure into a molten salt and by positioning it at the interface between salt and precipitated metal phosphate.
The phosphate industry is classified by IAEA as one of the Naturally Occurring Radioactive Materials (NORM) industry sectors most likely to require regulatory consideration. The production of phosphorous fertilizers constitutes the major activity in the industry, which can give rise to exposures of workers and the public through the handling and usage of phosphate rock and residues associated with processing. During the production process, when phosphate rock is digested with acid to produce phosphoric acid, some radionuclides, particularly Radium, become concentrated in residues, such as the scale that tends to form inside pipes and vessels. The registered radioactivity of phosphate rock in South Korea is less than 1.7 Bq/g for U-238, but according to the IAEA SRS No. 49, the radioactivity of phosphate scale can be up to 1,000 times higher than the raw mineral. Therefore, this study evaluated the potential for worker exposure during maintenance related to the removal of scales at a fertilizer manufacturing facility producing phosphoric acid in Korea.
In this study, we evaluated the performance of phosphate-functionalized silica in adsorbing uranium and provided insights into optimizing the initial conditions of the uranium solution (concentration and pH), which are often overlooked in uranium adsorption studies. While most studies take into account the effect of pH on both the surface charge of the adsorbents and the dissolved speciation of uranium in solution, they often overlook the formation of solid phases such as β-UO2(OH)2 (cr) and UO3· 2H2O(cr), leading to an overestimation of the adsorption capacity. To address this issue, we considered the speciation of U(VI) calculated using thermodynamic data. Our findings suggest that it is reasonable to evaluate the adsorption performance at pH 4 and concentration below 1.35 mM. The formation of β-UO2(OH)2 (cr) starts at 23 μM (pH 5) and 1 μM (pH 6) and increases sharply with increasing concentration. To avoid interference from the formation of solid phases, experiments should be conducted at lower concentrations, which in turn require very small msorbent/Vsolution ratios. However, controlling small amounts of sorbent can be challenging, and increasing the volume of the solution can generate significant amounts of radioactive waste. We also used UV-vis spectra analysis to investigate the formation of solid phases. We found that a 100 mg L-1 uranium solution resulted in the formation of colloidal particles in the solid phase after 2.5 hours at pH 6, while at pH 4, no significant changes in absorbance were observed over 120 hours, indicating a stable ion phase. Based on these conditions, we obtained an excellent adsorption capacity of 110 mg g-1.
PURPOSES : In this study, a method to use magnesium phosphate ceramic (MPC) concrete for the surface maintenance of airport pavements with jointed concrete is developed.
METHODS : To investigate the application of a material incorporated with MPC for the surface maintenance of airport pavements with jointed concrete, structures with various cross-sections and thicknesses were constructed. The cross-section of the structure was modeled for the surface maintenance of four types of pavements and typical pavement construction processes, such as cutting, cleaning, production and casting, finishing, hardening, and joint reinstallation. Subsequently, the hours required for each process was determined.
RESULTS : The MPC concrete used for the surface maintenance of airport pavements with jointed concrete demonstrate excellent performance. The MPC concrete indicates a compressive strength exceeding 25 MPa for 2 h, and its hydration heat is 52.9 ℃~61.2 ℃. Meanwhile, the crushing and cleaning performed during the production and casting of the MPC require a significant amount of time. Specifically, for a partial repair process, a total of 6 h is sufficient under traffic control, although this duration is inadequate for a complete repair process.
CONCLUSIONS : MPC concrete is advantageous for the surface maintenance of airport pavements with jointed concrete. In fact, MPC concrete can be sufficiently constructed using existing concrete maintenance equipment, and partial repair works spanning a cross-sectional area of 11 m2 can be completed in 1 d. In addition, if the crushing and cleaning are performed separately from production and construction, then repair work using MPC concrete can be performed at a larger scale.
The oxygen evolution reaction (OER) is very sluggish compared to the hydrogen evolution reaction (HER). Considering this difference is essential when designing and developing a cost-effective and facile synthesis method for a catalyst that can effectively perform OER activity. The material should possess a high surface area and more active sites. Considering these points, in this work we successfully synthesized sheets of cobalt phosphate hydrate (CP) and sulphurated cobalt phosphate hydrate (CPS) material, using simple successive ionic layered adsorption and reaction (SILAR) methods followed by sulfurization. The CP and CPS electrodes exhibited overpotentials of 279 mV with a Tafel slope of 212 mV dec1 and 381 mV with a Tafel slope of 212 mV dec1, respectively. The superior performance after sulfurization is attributed to the intrinsic activity of the deposited well-aligned nanosheet structures, which provided a substantial number of electrochemically active surface sites, speeded electron transfer, and at the same time improved the diffusion of the electrolyte.
Spent nuclear fuels are temporarily stored in nuclear power plant site. When a problem such as cracking of spent nuclear fuel assembly or cladding occurs or uranium that has not been separated during the reprocessing remains, it is necessary to treat it. The borosilicate glasses have been considered to vitrify whole spent nuclear fuel assembly. However, a large amount of Pb addition was necessary to oxidize metals in assembly to make them suitable for oxide glass vitrifcation. Furthermore, these borosilicate glasses need to be melted at high temperatures (> 1,400°C) when UO2 content is more than 20wt%. Iron phosphate glasses can be melted at a relatively low temperature (< 1,300°C) even with a similar UO2 addition. A composition of iron phosphate glass for immobilization of uranium oxide has been developed. The glasses have glass transition temperatures of ~555°C that are high enough to maintain its phase stability in geological repositories. The waste loading of UO2 in the glass is ~33.73wt%. Normalized elemental releases from the product consistency test were well below the US regulation of 2 g/m2. Nuclear criticality safety and heat generation in deep geological repositories were calculated using MCNP and computational fluid dynamics simulation, respectively. The glass had effective neutron multiplication factor (keff) of 0.755, which is smaller than the nuclear- criticality safety regulation of 0.95. Surface temperature of the disposal canister is expected to lower than the limit temperature (< 100°C). Most of the U in the glass is in the 4+state, which is more chemically durable than the 6+state. As a result of long-term dissolution experiment, chemically-durable uranium pyrophosphate (UP2O7) crystals were formed.
High-temperature friction performances of graphite blocks (GBs) and zinc phosphate impregnated graphite blocks (IGBs) were evaluated under various friction temperatures. The surface of IGB exhibited extremely lower average friction coefficient values, that was 0.007 at 400 °C and 0.008 at 450 °C, in comparison to that of GB (0.13 at 400 °C and 0.16 at 450 °C, respectively). The worn surface of IGB in the high-temperature friction test was smoother and more complete than that of GB. The wear under high temperature and load caused the transformation of zinc pyrophosphate to zinc metaphosphate and the formation of a continuous large-area boundary lubrication layer combined with graphite and metallic element on the wear surface. The superior tribology property of IGB could be attributed to the digestion of iron oxides by tribo-chemical reactions and passivation of the exposed dangling covalent bonds. Specifically, the layered structure generated on the IGB wear interface effectively decreased the adhesive forces and prevented the surface from serious damage.