Tributyl Phosphate Research Articles

Biodegradation of tri-butyl phosphate by Trametes versicolor and its application in a trickle bed reactor under non-sterile conditions

Tri-butyl phosphate (TBP) is a widely used organophosphate flame retardant. However, it is also regarded as emerging contaminant due to its various toxic effects and poor removal by conventional wastewater treatment. In present study, we investigated the degradation of TBP (10 mg/L) by the white rot fungus Trametes versicolor in both laboratory conditions and a trickle bed reactor (TBR) under non-sterile conditions. The removal yield reached 98 % after 3 days, during which the intracellular enzymatic system cytochrome P450 was involved. Four transformation products (TPs) were identified, namely dibutyl 3-hydroxybutyl phosphate, dibutyl phosphate, butyl 3-hydroxybutyl phosphate and butyl dihydrogen phosphate, which allowed us to propose a degradation pathway where hydroxylation and hydrolysis made considerable contribution. TBP treatment in the TBR with T. versicolor immobilized on wood chips operating in sequential batch mode with 10 cycles of 3 days reached average removals higher than 93 %, demonstrating the potential for practical application. Despite similar removal rates in heat-killed and abiotic controls (89 % and 97 %, respectively), global mass balance analysis indicated 86 %, 64 %, and 86 % removal by degradation in the fungal, heat-killed, and abiotic controls, respectively. Analysis of the microbial assemblage in solid phase suggested that the established bacterial populations displayed a synergistic effect with immobilized fungus. This study is the first to report on TBP degradation by T. versicolor in a TBR under non-sterile conditions, suggesting that this method could be a viable option for large-scale environmental applications.

Sustainable separation of molybdenum from mixed mineral acids generated as semiconductor industry waste streams using tributyl phosphate (TBP) by effects of hybrid machine learning models

This study explores the separation and optimization of molybdenum (Mo) from mixed mineral acids derived from semiconductor industry waste streams with tributyl phosphate (TBP) by implementing machine learning (ML) models. Considerable experimental tests were performed to evaluate the impact of various operational variables on the effectiveness of Mo extraction and stripping. The support vector regression (SVR) paired with harmony search algorithm (HSA), genetic algorithm (GA), and shuffled frog leaping algorithm (SFLA) were employed for enhancement in the separation process and structural optimization. The SVR-SFLA model yielded the most meticulous predictions, identifying optimal extraction conditions with a TBP concentration, mixing time, temperature, and O/A ratio of 50%, 30 min, 25 °C, and 1, respectively, achieving 77.8% efficiency. The derived results from the SVR-SFLA model, in tandem with the McCabe-Theil diagram, indicated a four-stage counter-current extraction process required to achieve a yield exceeding 99%. For the stripping process, the hybrid model indicated optimal conditions with 3 M NH4OH and an A/O ratio of 0.5 at 50 °C for 20 min, requiring two counter-current stages for nearly complete stripping. Feature importance analysis using a random forest algorithm (RFA) highlighted the NH4OH concentration and phase ratio as the most significant factors, contributing 40.3% and 29.1%, respectively, to the stripping from the loaded TBP phase. The final product, obtained after crystallization and thermal decomposition of the strip solutions, was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS), revealing 99.74% purity for molybdenum trioxide.

Removal of TBP sorbed on wood by Trametes versicolor through solid-state fermentation

The use of white-rot fungi is a promising approach for removing organophosphate flame retardants (OPFRs) from wastewaters. Immobilization in wood for this purpose ensures the predominance of the fungus but also contributes to OPFRs sorption. This work focused on the ability of T. versicolor to degrade tributyl phosphate (TBP) sorbed in wood. This initially underwent ten sorption cycles, each involving exposure to a 10mg · L-1 TBP solution. Throughout each cycle, the wood exhibited a sustained sorption capacity (0.035 ± 0.002mg TBP · g. dry wood-1 per cycle). The wood residues obtained after each sorption cycle were inoculated with T. versicolor. After 60 days of inoculation, fungus degraded over 90% of TBP in each cycle’s wood residue. However, fungal growth was inhibited, resulting in a 43% decrease in biomass compared to controls. The fact that biomass remained active and capable of degrading TBP suggests that the growth decrease is likely due to the formation of transformation products. An increase in toxicity units (from 13.64 to 87.86 at the end) was associated with the accumulation of 3-hydroxybutyl dihydrogen phosphate (OH-MBP). However, subsequent experiments demonstrated that given sufficient time, the fungus not only degraded OH-MBP but also produced a non-toxic effluent.

Elucidation of the Decomplexation and Reverse Migration Mechanism of Uranyl Ions from the Oil Phase to the Aqueous Phase Using Microsecond (0.2 μs) Molecular Dynamics Simulations.

Interphase ion transfer is ubiquitous in chemistry, physics, biology, and various engineering sciences. Ion transfer from the aqueous phase to the oil phase or vice versa is a complex chemical phenomenon, and its fundamental understanding is crucial for efficient and economical mass transfer. This ion transfer is much more complex for radionuclide metal ions. Therefore, an attempt has been made to elucidate the decomplexation and mechanism of reverse migration of uranyl ions from the loaded oil phase to the aqueous phase using large time-scale molecular dynamics simulations (microseconds) and density functional theory (DFT). The strength of the metal-ligand complex is the key factor for stripping among other mass transfer parameters. Stronger the metal-ligand complex, the lower the tendency for reverse migration into the aqueous phase, which was demonstrated by three different ligands for reverse migration using water as the stripping agent. The interaction energy of the metal-ligand complex has been calculated using DFT. The reverse migration is validated by the distance between the centers of mass. Higher interface thickness and lower interfacial tension belong to N,N,N',N'-tetra-octyldiglycolamide (TODGA), which are favorable for mass transfer across the liquid-liquid interface. The computed distribution coefficient (KD) is favorable for tributyl phosphate (TBP) and tri-iso-amyl phosphate (TiAP), whereas TODGA shows a higher KD, indicating a less favorable value for reverse migration. The distance between the uranyl ion and the TODGA molecule confirms that the entrapment of uranyl ions in the TODGA phase might be attributed to aggregation. Further, the aggregation tendency of TODGA molecules reduces the back extraction and the recovery of uranyl ions into the aqueous phase. The present MD results might be important for predicting an efficient back-extracting agent for the recovery of the metal ions from the oil phase.

Construction of Phenytoin Selective Electrodes and Its Application to Pharmaceutical Preparation

Phenytoin selective electrodes were constructed based on penytoin-phosphotungstate (Ph-PT) complex with different plasticizers; di-butyl phosphate (DBP), tri-butyl phosphate (TBP), di-butyl phthalate (DBPH),and o-nitro phenyl octyl ether (NPOE) phthalate. The electrodes based on DBPH, ONPOE plasticizers gave Narnistain slope which are, 56.4 and 55.3mV/decade with detection limit of 1.9x10-5 M , 1.8x10-5 and concentration range 10-1 to 10-4 M and pH range 3.0 – 8.0. The electrodes based on TBP and DBP showed non-Nernistain slopes, 40.2,40.5 mV/decade for both plasticizers. Interfering of some cations was investigated and shows no interfering with electrodes response. Potentiometric methods were used for measuring phenytion in pharmaceutical drugs (tablets) and the electrode based on DBPH was used for determination. The recovery obtained from measuring was in good agreements with that given in British Pharmacopeias.

Assessment of certain theoretical modeling for extraction data of uranium ion by loaded SM-7 with TBP using fixed bed column operation

Abstract Theoretical evaluation of experimental extraction data of U (VI) from nitric acid solutions by tri-n-butyl phosphate (TBP) loaded on macro reticular polymer SM-7 was verified using Thomas and Yan models. These data are represented by breakthrough relations at different conditions; flow rate, concentrations and interfering ions. Comparing correlation coefficients (R 2) of both models, it was found that R 2 equal 0.96 for Thomas model comparing to 0.88 for Yan one, indicating that Thomas model is convenient for evaluation of that extraction process. The calculated, theoretically, value of (q Th) was found to be almost equal to (qexp ) the practical one.

Gamma Radiolysis of n‐Dodecane: Physicochemical Properties and Metal Retention Behavior

AbstractThe gamma radiolytic degradation behavior of n‐dodecane (n‐DD) was investigated under conditions both with and without the presence of nitric acid. The physicochemical property alterations due to radiolysis were quantified and compared against an unirradiated system. Compositional changes in n‐DD post radiolysis was measured, and the degraded n‐DD was characterized using Fourier‐transform infrared (FT‐IR) spectroscopy, gas chromatography (GC), and gas chromatography–mass spectrometry (GC–MS) analysis. The presence of nitric acid was observed to accelerate the radiolytic degradation of n‐DD. The extent of diluent degradation caused by gamma irradiation was assessed through the retention behavior of uranium [U(VI)], plutonium [Pu(IV)], and zirconium [Zr(IV)] in 1.1 M tri‐n‐butyl phosphate (TBP) in irradiated diluent. Furthermore, the effectiveness of hydrazine carbonate (HC) as a solvent wash reagent for the removal of diluent degradation products was evaluated.

A green approach coupled with molecular dynamics simulations and toxicity assays to infer the mode of action for organophosphate esters

Organophosphate esters (OPEs) have attracted extensive attention due to their toxic effects on human health and biological systems as plasticizers and flame retardants. This study focused on exploring a green approach to get toxicity mechanisms that used less solvents or organisms. The toxicity values of selected organophosphate esters including tri (2-chloroethyl) phosphate (TCEP), tri (1, 3-dichloro-2-propyl) phosphate (TDCP), tripropyl phosphate (TPrP), tri-n-butyl phosphate (TnBP), and tritolyl Phosphate (TCrP) to Photobacterium phosphoreum were determined. Their EC50 range was between 7.27 × 10−8–5.12 × 10−6 mol/L. Based on molecular dynamics simulation the data of binding affinity between OPEs and n-octanol / phospholipid bilayer were calculated respectively. Coupling with binding affinity energies and toxicity values, the mode of action (MOA) of OPEs including types of reactive or anesthetic mechanism could be fast deduced. The proposed hypothesis of n-octanol (C8H18O) as a virtual biofilm to replace phospholipid bilayer was verified. The alternative green approach could simplify toxicity assay and realize fast predicting MOA for different chemicals and model organisms.

Highly enhanced fluoride removal from aqueous systems via solvent extraction utilizing trialkyl phosphine oxide as an efficient extractant

Solvent extraction (SX) has been recognized as an efficient approach for the large-scale removal of impurities, demonstrating considerable potential for fluoride extraction in industrial applications. However, existing fluoride extraction methods typically require the incorporation of additives to form complexes with fluoride for its removal. Due to the excessive additive requirements for efficient fluoride removal, these methods inevitably result in secondary contamination of feed solution, necessitating additional purification efforts to remove them. In this study, four extractants (trioctyl amine, tributyl phosphate, trioctyl phosphate, and trialkyl phosphine oxide (TRPO)) were investigated for fluoride removal via hydrogen bonding with hydrofluoric acid (HF). Various parameters, including the concentrations of extractants and stripping agents, pH values, extraction time, and temperature were initially optimized. It was found that TRPO exhibits the highest extraction efficiency for HF, with a single-stage extraction rate exceeding 70 %. Complete fluoride removal (> 99.9 %) was achieved through a consecutive four-stage extraction process. Further experiments, including maximum loading and slope analysis, combined with FT-IR and 19F NMR characterization, and DFT calculations elucidate the mechanism of the extraction. The transfer of HF into the organic phase is accomplished by the formation of a 1:1 hydrogen-bonded complex with TRPO. The loaded fluoride in the organic phase can be easily stripped by a base to get a fluoride salt. This study paves the way for the construction of novel SX systems to remove fluoride as HF.

STUDIES THE CRUCIAL ROLE OF SELECTION OF EXTRACTANT TO EXTRACT NIOBIUM FROM SULFURYL FLUORIDE SOLUTION AND OPTIMIZATION OF EXTRACTION CONDITIONS

The increasing demand for rare refractory metals such as niobium in high-tech industries requires the development of efficient and sustainable methods to extract them from secondary sources, including industrial by-products. This study studied niobium extraction from a fluoride-sulfuric acid solution obtained by leaching a niobium-containing intermediate product. A comprehensive assessment of various organic extractants, including methyl isobutyl ketone, tributyl phosphate, trioctylamine, and Cyanex 923, was performed, focusing on the recoverability of niobium from this solution. Experimental results show that Cyanex 923 is significantly superior to other extractants in efficacy. The extraction of niobium at different concentrations of this extractant in toluene and the ratios of organic and aqueous phases were studied. It is established that an increase in the contact time of the phases does not contribute to additional niobium recovery. Studies show that applying concentrated Cyanex 923 in toluene ensures complete recovery of niobium into the organic phase. The three-stage counter-current extraction shows a slightly higher niobium recovery efficiency than the single-stage process.

Alkaline Hydrolysis of Tri-iso-amyl Phosphate in n-dodecane Using Sodium Hydroxide: Part 1—Factors Affecting the Hydrolysis Process

Tri-iso-amyl phosphate (TiAP) is being proposed as a suitable alternate to tri-butyl phosphate mainly for the reprocessing of high-Pu-content spent fuel from fast reactors. After its use in a few cycles, the solvent has to be categorized as organic waste, which needs further treatment and disposal. Toward this, systematic studies have been carried out on the alkaline hydrolysis of TiAP in n-dodecane (n-DD) using sodium hydroxide (NaOH). The experiments were carried out in a stainless steel autoclave with a reactor vessel having a 1 L processing capacity. The parameters, such as mixing intensity, temperature, aqueous-to-organic phase volume ratio, and initial NaOH concentration, that can affect the kinetics of the hydrolysis reaction were studied. During each experiment, the TiAP concentration in the organic phase decreased steadily with time followed by a sudden decrease, which could be due to the autocatalytic hydrolysis of TiAP. After the completion of the hydrolysis reaction, the organic phase was mainly n-DD with iso-amyl alcohol, suggesting complete hydrolysis of TiAP to its aqueous-soluble hydrolysis products. Based on the studies, it was observed that temperature and initial NaOH concentration, among other parameters, highly influence the rate of hydrolysis of TiAP.

Chemical profiling of organic contaminants in rural surface waters combining target and non-target LC-HRMS/MS analysis

The pollution of natural waters by contaminants of emerging concern (CECs) is one of the pressing problems due to their global distribution and potential negative effects on the environment and human health. In rural areas with lower population density and limited industrial development, less contamination is expected. However, the lack of wastewater treatment plants (WWTPs) or their poor removal efficiency can lead to significant input of pollutants. In this context, 11 streams of rural areas in the Guadalquivir River basin, southeast of Spain, were studied over two years to obtain an overview of the origin and distribution of contaminants. A target method using solid-phase extraction and liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) was developed for the analysis of 316 compounds in surface waters. A total of 78 target analytes were detected, comprising pesticides, pharmaceuticals, personal care products (PCPs), transformation products (TPs), and industrial chemicals. The flame retardant tributyl phosphate (16–3572 ng L−1) was detected in all samples, followed by caffeine (30–8090 ng L−1) and the analgesic tramadol (3–1493 ng L−1). The target approach was combined with a non-target analysis (NTA) strategy to obtain an overall perspective of the chemical profile of unexpected or unknown compounds in the samples. Up to 79 contaminants were tentatively identified, and 12 of them were finally confirmed with standards. Most of the contaminants determined by NTA were pharmaceuticals and their TPs. The results indicated that most of CECs have an urban origin despite traditional agriculture is the main economic activity in this region. Moreover, the absence of WWTPs in small towns is significant, as contamination levels at these sites were comparable to or higher than those in larger populations with sewage treatments.

Effect of Electric Fields on the Decomposition of Phosphate Esters.

Phosphate esters decompose on metal surfaces and form protective polyphosphate films. For many applications, such as in lubricants for electric vehicles and wind turbines, an understanding of the effect of electric fields on molecular decomposition is urgently required. Experimental investigations have yielded contradictory results, with some suggesting that electric fields improve tribological performance, while others have reported the opposite effect. Here, we use nonequilibrium molecular dynamics (NEMD) simulations to study the decomposition of tri-n-butyl phosphate (TNBP) molecules nanoconfined between ferrous surfaces (iron and iron oxide) under electrostatic fields. The reactive force field (ReaxFF) method is used to model the effects of chemical bonding and molecular dissociation. We show that the charge transfer with the polarization current equalization (QTPIE) method gives more realistic behavior compared to the standard charge equilibration (QEq) method under applied electrostatic fields. The rate of TNBP decomposition via carbon-oxygen bond dissociation is faster in the nanoconfined systems than that in the bulk due to the catalytic action of the surfaces. In all cases, the application of an electric field accelerates TNBP decomposition. When electric fields are applied to the confined systems, the phosphate anions are pulled toward the surface with high electric potential, while the alkyl cations are pulled to the surface with lower potential, leading to asymmetric film growth. Analysis of the temperature- and electric field strength-dependent dissociation rate constants using the Arrhenius equation suggests that, on reactive iron surfaces, the increased reactivity under an applied electric field is driven mostly by an increase in the pre-exponential factor, which is linked to the number of molecule-surface collisions. Conversely, the accelerated decomposition of TNBP on iron oxide surfaces can be attributed to a reduction in the activation energy with increasing electric field strength. Single-molecule nudged-elastic band (NEB) calculations also show a linear reduction in the energy barrier for carbon-oxygen bond breaking with electric field strength, due to stabilization of the charged transition state. The simulation results are consistent with experimental observations of enhanced and asymmetric tribofilm growth under electrostatic fields.

Occurrence and Distribution of Organophosphate Flame Retardants in Tap Water System-Implications for Human Exposure from Shanghai, China.

The pollution of organophosphate flame retardants (OPFRs) is of global concern, but the site-specific data of OPFR concentrations in drinking water are scarce for many areas of the world outside of Europe and the US. This study aimed to investigate the occurrence and profiles of OPFRs in the tap water treatment and delivery process in Shanghai. In total, 106 samples were analyzed for 10 OPFRs, which were collected periodically from monitoring points of drinking water treatment plants and piped water between November 2021 and July 2023. The average daily doses of OPFRs through the ingestion of tap water were calculated by multiplying nominal volumes of water ingestion rates with the measured concentrations of OPFRs. Hazard quotients, the hazard index, and the carcinogenic risks of OPFRs via drinking water were used to estimate the health risks. Tributyl phosphate (TBP), tris(2-chloroethyl) phosphate (TCEP), and tris (1-chloro-2-propyl) phosphate (TCIPP) were found in >90% of the tap water samples, whereas triethyl phosphate (TEP) and tris (2,3-dibromopropyl) phosphate (TDBPP) were not found in any samples. The concentrations of Σ10OPFRs were found at part-per-trillion ranges, with average concentrations that ranged from 86.0 ng/L in February 2023 (dry season) to 218 ng/L in July 2022 (wet season). TCIPP was the most abundant compound among the investigated OPFRs. The average daily dose of Σ10OPFRs via the ingestion of tap water was up to 20.4 ng/kg body weight/day. The hazard quotients of OPFRs through drinking water were in the range of 10-5-10-4, indicating low risk levels. Moreover, the hazard index of OPFRs indicated that the risk for children (2 × 10-4) was higher than adults (7 × 10-5). Tap water intake may be an important source of OPFRs exposure. But the risk of OPFRs for local residents is at a low level through drinking water.

Identification of Primary Organophosphate Esters Contributing to Enhanced Risk of Gestational Diabetes Mellitus Based on a Case-Control Study.

Epidemiological studies on associations of organophosphate ester (OPE) exposure and gestational diabetes mellitus (GDM) risk, which remain rare and inconclusive, were carried out with a case-control population comprising 287 GDM and 313 non-GDM pregnant women recruited from Tianjin. The GDM group suffered distinctly higher serum concentrations of tri-n-butyl phosphate (TNBP), tri(2-butoxyethyl) phosphate (TBOEP), triphenyl phosphate (TPHP), tri-iso-propyl phosphate (TIPP), and tri(1-chloro-2-propyl) phosphate (TCIPP) than the healthy control group (p < 0.001). Traditional analysis methods employed for either individual or mixture effects found positive correlations (p < 0.05) between the concentrations of five OPEs (i.e., TNBP, TBOEP, TPHP, TIPP, and TCIPP) and the incidence of GDM, while 2-ethylhexyl diphenyl phosphate, tri(1-chloro-2-propyl) phosphate, and bis(2-ethylhexyl) phosphate exhibited opposite effects. Three machine learning methods considering the concurrence of OPE mixture exposure and population characteristics were applied to clarify their relative importance to GDM risk, among which random forest performed the best. Several OPEs, particularly TNBP and TBOEP ranking at the top, made greater contributions than some demographical characteristics, such as prepregnancy body mass index and family history of diabetes, to the occurrence of GDM. This was further validated by another independent case-control population obtained from Hangzhou.

Highly selective extraction of aluminum from chloride and sulfate solutions using a mixture of alkoxycarboxylic acid and tributyl phosphate

Four different solvent extraction systems are compared for aluminum (Al) separation in the presence of alkali metals, alkaline-earth metals, and transition metals. The octoxyacetic acid (OOA acid) is utilized as an Al extraction reagent for the first time, exhibiting high selectivity for Al. The impacts of the concentration of extractants, the equilibrium pH of the aqueous phase, and the concentration of phase modifier were studied systemically. The results indicate that the Al extraction efficiency using OOA/TBP (tributyl phosphate) system could reach 98.9 ± 0.63 % via a single-step solvent extraction process while maintaining negligible extraction for the other metal ions at the pH value of ∼ 4.2. Meanwhile, the separation factors (β) of Al over magnesium, calcium, manganese, cobalt and nickel reach the maximum values (βAl/Mg = 285157, βAl/Ca = 18275, βAl/Mn = 19271, βAl/Co = 10814, βAl/Ni = 5969). Slope analysis and infrared spectroscopic characterization confirm that the extraction of Al by the OOA/TBP system follows the cation exchange mechanism. The OOA/TBP solvent extraction system is promising for the efficient separation of Al, with potential applications in a wide range of practical scenarios.

Characteristics and Performance of Cerium Extraction from Cerium Hydroxide Concentrate using Tri Butyl Phosphate

Characteristics and Performance of Cerium Extraction from Cerium Hydroxide Concentrate using Tri Butyl Phosphate

Occupational Exposure of On-Shift Ottawa Firefighters to Flame Retardants and Polycyclic Aromatic Hydrocarbons.

Firefighters can be exposed to complex mixtures of airborne substances, including hazardous substances released during structural fires. This study employed silicone wristbands (SWBs) as passive samplers to investigate potential exposure to polycyclic aromatic hydrocarbons (PAHs) and flame retardants (FRs). SWBs were deployed at different areas of four fire stations, in four truck cabins, and at an office control location; they were also donned outside the jackets of 18 firefighters who responded to fire calls. Overall, office areas had significantly lower PAHs than fire station areas. Vehicle bays and truck cabins had significantly higher concentrations of low molecular weight (LMW) PAHs than sleeping and living room areas. For organophosphate ester flame retardants (OPFRs), tri-n-butyl phosphate (TnBP) and tris(1-chloro-2-propyl) phosphate (TCPP) were detected in all the samples; 2-ethylhexyl diphenyl phosphate (EHDPP) was more frequently detected in the fire station areas. Triphenyl phosphate (TPP) concentrations were highest in the truck cabin and office areas, and tris(1,3-dichloro-2-propyl)phosphate (TDCPP) was highest in truck cabins. Thirteen of 16 PAHs and nine of 36 OPFRs were detected in all the SWBs worn by firefighters, and tris (2-butoxyethyl) phosphate (TBEP) was the predominant OPFR. Levels of LMW PAHs were significantly lower when firefighters did not enter the fire. LMW PAHs, HMW (high molecular weight) PAHs, and EHDPP were significantly elevated when heavy smoke was reported. This work highlights the potential for occupational exposure to PAHs and flame retardants in some fire station areas; moreover, factors that may influence exposure during fire suppression. Whilst firefighters' occupational exposure to PAHs is likely related to fire suppression and exposure to contaminated gear and trucks, exposure to OPFRs may be more related to their presence in truck interiors and electronics.

Three-liquid-phase behavior in the quaternary systems of water + phosphoric acid + diisopropyl ether + tributyl phosphate/methyl isobutyl ketone at 298.2 K

The three-liquid-phase formation in the ternary system of water + phosphoric acid + diisopropyl ether (DIPE) makes the phosphoric acid extraction only effective for acid mass fractions above 0.69. To avoid the undesirable formation of the third phase and enhance acid extraction, particularly at low concentrations, two phase modifiers, methyl isobutyl ketone (MIBK) and tributyl phosphate (TBP), were systematically studied. In order to quantify the synergetic effect of the mixed solvents of DIPE+TBP and DIPE+MIBK, the liquid–liquid equilibria for the quaternary systems of H2O+H3PO4 + DIPE+TBP and H2O+H3PO4 + DIPE+MIBK were fully established for different DIPE/phase modifier (TBP or MIBK) mass ratios (90/10, 70/30, 50/50, and 20/80) at 298.2 K under atmospheric pressure using the cloud point and Othmer graphical method. Othmer-Tobias and Hand correlations were used to fit the tie-line data and assess its consistency. In addition, the behavior of the three-phase zone was also studied as a function of the phase modifiers content. Separation factor (S) and acid distribution (D2) were used to identify the most effective solvent with the potential to enhance phosphoric acid extraction from aqueous solutions.

Flow characteristics and mass transfer performance of phosphoric acid extraction in a T-type central plug-in microreactor

In recent years, the demand for phosphoric acid, a key raw material for lithium iron phosphate batteries, has surged. However, current phosphoric acid extraction equipment faces challenges such as low mass transfer efficiency and difficulty in phase separation, leading to reduced production efficiency, bulky equipment, and scaling issues. To address these problems, this study introduces a T-type central plug-in microreactor (TCPM) designed to enhance mass transfer efficiency and facilitate rapid phase separation. The extraction of phosphoric acid from the water phase to the organic phase (volume ratio of tributyl phosphate to kerosene is 4:1) was chosen as the experimental system. We investigated the effects of various parameters on liquid-liquid flow and mass transfer characteristics in the TCPM. Visualization techniques identified slug and parallel flow as the primary liquid-liquid flow patterns within the TCPM. Notably, the central plug-in promotes the formation of parallel flow, improving phase separation compared to conventional T-type microreactors. The volume mass transfer coefficient of the TCPM ranges from 0.023 to 0.074 s-1, and the optimal phosphoric acid extraction efficiency and volume mass transfer coefficient can reach up to 90.5% and 0.074 s-1, respectively, outperforming conventional T-type microreactors. Predictive model for extraction efficiency was developed, showing deviations within 10%. These findings demonstrate the TCPM's potential as an efficient phosphoric acid extraction device with rapid phase separation, holding significant promise for liquid-liquid extraction applications.