查找使用阿拉丁产品的科研文献

Lithium extraction from synthetic brine with high Mg2+/Li+ ratio using the polymer inclusion membrane

Chengyi Zhang,Yingxin Mu,Song Zhao,Wen Zhang,Yuxin Wang

Lithium extraction from brines with the high Mg 2+ /Li + ratio is crucial for sustainable lithium resource and environmental protection. This study incorporated the classic tributylphosphate (TBP)/FeCl 3 system into the polyvinyl chloride (PVC) based polymer inclusion membrane (PIM) to extract Li + from the solution which is rich of Mg 2+ (The initial Mg 2+ /Li + molar ratio is 15). The morphology and composition of PIMs were characterized systematically, and the content of TBP/FeCl 3 carrier in the PIM was optimized. Compared to liquid-liquid extraction, the extraction ratio of Li + for PIM extraction increases by 20% and the separation factor of Li + over Mg 2+ increases by 5%. Besides, the loss ratio of Fe 3+ after one loop of liquid-liquid extraction is 17.79%, which is close to that of PIM extraction after three loops (18.30%), demonstrating that the PIM showed a good stability. Furthermore, the separation factor of Li + over Mg 2+ for the PIM with 50 wt% TBP/FeCl 3 is as high as 176 and the initial flux for Li + is 8.12 × 10 −4  mol m −2  h −1 . This study displays a TBP/FeCl 3 based PIM with high selectivity for Li + , providing a possible membrane technology for lithium extraction from brines.

Separation and recovery of uranium and beryllium from acidic sulphate solutions by solvent extraction using mixture of organophosphonic extractants

Xia Hongyang,Zheng Boyuan,Zhao Xu,Huang Yanting,Wang Hongqiang,Hu Eming,Lei Zhiwu,Hu Fang,Wang Qingliang

Uranium (U) and beryllium (Be) are strategic critical metals. It is imperative to realize the comprehensive utilization of U or Be poly-metallic resources. This study employed solvent extraction to separate and recover U and Be from a simulated acidic sulphate leachate from a U-Be associated ore. The results indicated that the mixture extractant system containing bis-(2-ethylhexyl) phosphoric acid (D2EHPA) and tributyl phosphate (TBP) had affinity for U, and the selectivity of U towards Be was dependent on the hydrogen ion concentration of the solution. 99.74% U and 6.98% Be were extracted with a two-stage counter-current extraction at sulfuric acid concentration of 1.58 mol/L. By using 2 mol/L Na 2 CO 3 solution as the stripping solution, 94.79% U was stripped from the U-loaded organic phase with a one-stage stripping process. After adjusting the pH of the raffinate to 2, with D2EHPA as extractant, 99.76% Be was recovered by performing a two-stage counter-current extraction. Besides, Be could be well stripped from the Be-loaded organic phase with 3 mol/L NaOH solution. And the stripping rate of Be reached 98.85% with a one-stage stripping process. The established method to separate U and Be from sulphate solutions with high acidity has several advantages, including recyclable, reliable, and environmentally friendliness, providing a promising new pathway for the green recovery of U and Be from poly-metallic resources.

Intensification of esterification process in TBP synthesis by in situ vapor stripping

Yuqiang Zhang,Jun Li,Yang Jin,Ming Chen,Defang Yu

BACKGROUND Over the past few decades, tri-n-butyl phosphate (TBP) has been a widely used and irreplaceable extractant that can extract a variety of heavy metal ions and inorganic acids. The conventional process of tri-n-butyl phosphate synthesis has the problem of low yield. The in situ vapor stripping method was developed to intensify the tri-n-butyl phosphate synthesis reaction. RESULTS In this work, the coupling process of in situ vapor stripping and reaction was proposed for the first time in the process of synthesis of TBP. It was found that the reaction of high concentration hydrogen chloride and 1-butanol would produce water, which resulted in increasing the possibility of side reactions, especially when the temperature was higher than 55 °C. In the lower temperature range, n-pentane was selected as the stripping medium, which effectively removed hydrogen chloride from the reaction system by in situ vapor stripping. The FT-IR analysis confirmed that TBP can be synthesized successfully by the vapor stripping process. In addition, the effects of n-pentane volume, temperature and stripping time on the yield of TBP and the amount of hydrogen chloride stripped were investigated. By applying the optimum reaction conditions, the yield of TBP was increased to 94%, larger than that of the current industrial process whose yield is only 80%. CONCLUSION The in situ vapor stripping process is demonstrated to be an effective method for intensification of the esterification process in TBP synthesis. It can be used for other reactions which generate volatile gases as the byproduct. © 2018 Society of Chemical Industry

Bright Alloy CdZnSe/ZnSe QDs with Nonquenching Photoluminescence at High Temperature and Their Application to Light-Emitting Diodes

Tingting Zhang,Xugu Zhang,Peizhi Yang,Jinke Bai,Chun Chang,Xiao Jin,Feng Zhao,Yan Huang,Feng Li

Stable luminance properties are essential for light-emitting devices with excellent performance. Thermal photoluminescence (PL) quenching of quantum dots (QDs) under a high temperature resulting from a surface hole or electron traps will lead to unstable and dim brightness. After treating CdZnSe/ZnSe QDs with TBP, which is a well-known passivation reagent of the anions, the excess Se sites on the surface of the QDs were removed and their PL quantum yields (QYs) was improved remarkable. Furthermore, after TBP treatment, the CdZnSe/ZnSe QDs exhibit no quenching phenomena even at a high temperature of 310°C. The electroluminescent light-mitting diodes based on the QDs with TBP treatment also demonstrated satisfied performance with a maximum current density of 1679.6 mA/cm2, a peak luminance of 89500 cd/m2, and the maximum values of EQE and luminescence efficiency are 15% and 14.9 cd/A, respectively. The performance of the fabricated devices can be further improved providing much more in-depth studies on the CdZnSe/ZnSe QDs.

An experimental study on the extraction mechanisms of Ce(IV) from HNO3 solutions using C4mimNTf2 as extractant

Li Chunhui,He Hui,He Mingjian,Gao Yang,Zhang Meng,Jiao Caishan

A detailed extraction equilibrium study is experimentally performed to understand the extraction mechanisms of Ce(IV) by 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (C 4 mimNTf 2 ) in 1,2-dichloroethane. Further, the influence of adding TBP on the distribution ratio is investigated and demonstrated. The ceric aqueous chemistry in the nitric acid solution and slope analysis are combined to reveal the extraction mechanism. The monovalent anionic complex HCe(NO 3 ) 6 − is the dominant species, which extracted by C 4 mimNTf 2 . Importantly, this study demonstrates the antagonistic effect between TBP and C 4 mimNTf 2 on the extraction process.

Preferentially selective lithium recovery from spent lithium-ion battery leachates using NaBPh4/TBP synergistic extraction

Qian Cheng,Yue Wang,Yongxiang Wang,Panfeng Gao,Jun-Tao Li,Jiangxue Long,Haiyan Fu

Preferential Li extraction was achieved from spent lithium-ion battery leachates. • Complete separation of Li from Ni, Co, and Mn was achieved. • NaBPh₄ and TBP exhibit a significant synergistic effect on Li extraction. • The organic phase achieved 98.3% Li extraction via five-stage extraction. • Li in the stripped solutions was precipitated as pure Li 3 PO 4 . Effective recycling of spent lithium-ion batteries (LIBs) is vital for metal recovery. However, poor lithium (Li) purity and recovery efficiency highlight the need to develop new extractants for preferential Li recovery. In this work, a synergistic solvent extraction system consisting of sodium tetraphenylborate (NaBPh₄), tributyl phosphate (TBP) and 2-octanone was developed for the selective extraction of Li + from pretreated spent LIB leachates containing Li + , Ni 2+ , Co 2+ and Mn 2+ . Key operating parameters including initial Li + concentration, solution pH value, NaBPh 4 -to-Li + molar ratio, TBP volume fraction, organic-to-aqueous (O/A) volume ratio, and extraction time were systematically investigated. Under the optimized conditions, a five-stage extraction achieved a total Li + recovery of 98.3%. The loaded Li + in the organic phase was completely stripped using 0.5 mol/L HCl at an O/A volume ratio of 0.5, with a stripping efficiency of 100%. The stripped organic phase could be regenerated by supplementing NaBPh₄ at an optimal molar ratio n(NaBPh₄)/n(Li + ) = 5.5. FTIR and slope analysis revealed a distinct synergistic mechanism: NaBPh₄ initially combines with TBP to form a [(NaBPh₄)(TBP)] adduct, followed by ion exchange between Li + and Na + to generate [(LiBPh₄)(TBP)]. The prominent steric hindrance of NaBPh₄ effectively suppressed the co-extraction of Ni 2+ , Co 2+ and Mn 2+ , enabling outstanding Li + selectivity. Finally, Li + was recovered as Li₃PO₄ with 99.9% purity and 98.6% yield, whereas the raffinate containing Ni 2+ , Co 2+ , and Mn 2+ was suitable for producing ternary precursor materials. This work presents a simplified and sustainable “Li-first” strategy with strong potential for efficient and selective metal recovery from spent LIBs. Download: Download high-res image (126KB) Download: Download full-size image

TBP-MNPK combinations: a promising approach for selective Lithium extraction from high Mg/Li ratio liquids

Fan Li,Xiumin Yang,Zaolong Zhang,He Xiao,Junlian Wang

To address the third-phase formation and high-acidity stripping corrosion of the traditional TBP-FeCl₃ system for Li extraction from high Mg/Li ratio salt-lake brines, this study developed a TBP-MNPK-kerosene-FeCl₃ system using 2-heptanone (MNPK) as a modifier. MNPK eliminated third-phase formation and enabled complete phase separation within 50s. Under optimal conditions (20  vol % kerosene, 40  vol % TBP), Li extraction efficiency reached 85.4 % with a Li/Mg separation factor of 315. After water scrubbing and 3 mol/L HCl stripping, the stripping solution had 5.46 g/L Li (3.12-fold enrichment) and Li/Mg ratio of 11.38. This system provides an efficient, industrial-feasible Li extraction solution.

Developing a green lithium extraction process: insights into the TBP - P507 system and its industrial potential

Huifang Li,Shuo Wang,Wenbin Fan,Dahuan Liu

Solvent extraction has emerged as a highly promising method for lithium extraction . In this study, a sustainable extraction system was developed using 2-ethylhexyl phosphate mono 2-ethylhexyl ester (P507) and tri-butyl phosphate (TBP). By precisely controlling the coordination mode of Fe 3+ with TBP and P507 during the stripping process, a green extraction process was achieved. The research comprehensively investigated the effects of various factors, such as the type of diluent, saponification ratio, volume ratio of TBP, molar ratio of Fe/Li, and extraction phase ratio. Through systematic experiments, the optimal parameters were identified, and the coordination mechanism between the organic compounds and metal ions was elucidated. This work not only provides a promising approach for lithium recovery from salt lake brines but also establishes a solid theoretical foundation for the industrial application of the TBP-P507 extraction system, thereby holding great potential for promoting the development of the lithium extraction industry.

Construction and Performance Evaluation of a Bifidobacterium Delivery System Based on TBP-SA Pickering Emulsion Gels

An emulsion gel (EG-B) was fabricated through in situ calcium crosslinking of Pickering emulsions stabilized by tartary buckwheat protein–sodium alginate (TBP-SA) nanocomplexes for the encapsulation and delivery ofBifidobacterium longum. Control samples, including free bacteria (Free-B), Pickering emulsions (PE-B), and oil-free hydrogels (HG-B), were used to assess encapsulation efficiency, microstructure, rheological properties, thermal stability, dilution stability, gastrointestinal resistance, storage stability, and colonic adhesion of EG-B. The EG-B exhibited a dual structure comprising a compact Pickering interfacial membrane and a continuous calcium alginate gel network with solid-like rheology (G′>>G″) and viscosity of approximately 100 Pa·s, achieving 92.66% encapsulation efficiency. Viable counts exceeded 6 log CFU/g after pasteurization (72 °C, 15 s) and reached 6.12 log CFU/g post-simulated gastrointestinal digestion, significantly surpassing those of PE-B (5.12 log CFU/g) and HG-B (4.45 log CFU/g). Furthermore, EG-B displayed the highest viable retention during 14-day storage at 4 °C and 25 °C, along with a greater colonic adhesion efficiency (55.64%) compared to PE-B (47.09%) and HG-B (44.65%). The combination of interfacial stabilization and gel network formation provided by the TBP-SA complex presents a straightforward, food-grade strategy for probiotic delivery.

Mechanisms for the separation of Li+ and Mg2+ from salt lake brines using TBP and TOP systems

Yaoxian Hu,Hui Su,Zhaowu Zhu,Minxiu Zhou,Tao Qi

The tributyl phosphate (TBP)/FeCl 3 system has been widely used for lithium extraction from high‑magnesium salt lakes. However, at high TBP concentrations, the Li/Mg selectivity is significantly lower. This study revealed that at high TBP concentrations, TBP alone extracted Mg 2+ to form MgCl 2 ·6TBP as the main product, thus affecting the extraction efficiency of Li + . On this basis, a neutral phosphate with long carbon chains, trioctyl phosphate (TOP), was used to replace TBP. The separation capacity and extraction mechanism of the TOP/FeCl 3 system were studied, and density functional theory (DFT) calculations were employed to model the cationic complexes of the TOP and TBP systems. The results showed that in the presence of FeCl 3 , the extraction efficiency of Li + (E Li ) reached 91 %, and the Li/Mg separation factor (β Li/Mg ) was 5688. In contrast, in the TBP/FeCl 3 system with the same concentration, the E Li and β Li/Mg values were much lower at 74 % and 239, respectively. Furthermore, the TOP complex of Li + had shorter Li − O bond lengths and a more negative binding energy, while that formed with Mg 2+ had longer Mg − O bond lengths and the smallest HOMO–LUMO gap, indicating that TOP bonded more stably with Li + and was less prone to Mg 2+ extraction than TBP.

Study on the degradation of gelled tributyl phosphate combined with DFT calculations in a ternary Li2CO3-Na2CO3-K2CO3 molten salt system

Guanqing Hu,Qingguo Zhang,Yongde Yan,Yun Xue,Fuqiu Ma,Yuelin Wang,Xin Liu,Jinlong Song

With the rapid development of the global nuclear industry, substantial amounts of radioactive tributyl phosphate (TBP) have accumulated during the PUREX process. Prolonged accumulation poses significant environmental risks. Therefore, this study proposes an efficient molten salt oxidation (MSO) method for the treatment of gelled TBP. Comprehensive thermal analysis data indicate that the oxidation process of gelled TBP primarily consists of three stages. The composition of the waste salts after the MSO process was analyzed using X-ray diffraction spectroscopy. Fourier transform infrared spectroscopy revealed that the primary functional groups in gelled TBP were progressively degraded with increasing temperature. Scanning electron microscopy clearly illustrated the decomposition process of gelled TBP. X-ray photoelectron spectroscopy results identified the predominant forms of residual substances. The generated exhaust gas was analyzed using gas mass spectrometry and chromatography. Additionally, through DFT calculations of TBP, the possible reaction mechanism of TBP in the molten salts was deduced. In the molten state, carbonate can effectively absorb P 2 O 5 and eventually form stable NaPO 3 , which is the reason for the 94.90 % retention rate of phosphorus element. During the experimental process, the degradation rate of gelled TBP reached as high as 99.99 %. The MSO method proposed in this study shows great potential for the treatment of liquid organic waste.

Design of Ionic Lock Structure for a tBP-Free and Green-Solvent-Processed Hole Transporter in Perovskite Solar Cells

Ziwu Ding,Zilong Zhang,Yaqing Zou,Xiaofeng Li,Xiaolei Lin,Chunming Liu,Can Wang,Yong Chen,Xiaozhen Huang,Liangliang Zhang,Hongfang Du,Yue Wang,Mingwei An,Peng Gao,Yang Wang

Perovskite solar cells (PSCs) employing 2,2″,7,7″-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9’-spirobifluorene (Spiro-OMeTAD) as the hole-transporting material (HTM) often suffer from dopant-induced instabilities, including lithium (Li) salt aggregation, ion migration, and the volatilization of tert-butylpyridine (tBP). Additionally, the solution processing of conventional HTMs typically relies on toxic solvents, posing environmental and industrial challenges. In this study, we introduce an “ionic lock” strategy by incorporating polyoxygenated side chains─such as crown ether and 2-methoxyethoxy groups─into the backbone of conjugated hole conductors. The resulting HTMs, MPA-NDTCE and MPA-NDTME, exhibit excellent solubility in eco-friendly solvents like 3-methylcyclohexanone (3-MC) and demonstrate favorable compatibility with Li-based dopants. Notably, MPA-NDTCE shows enhanced molecular ordering, superior hole mobility, and stronger interactions with Li+ ions, facilitating dopant immobilization and stabilizing the film morphology. Consequently, PSCs utilizing MPA-NDTCE as a green-solvent-processable HTM achieve a high power conversion efficiency of 22.6%, coupled with robust thermal stability under aging at 65 °C. These improvements are attributed to the elimination of tBP and the effective suppression of Li-ion migration.