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Metals · 2025 ·Vol. 15 ·期 5 ·468 · IF 2.5

Selective Extraction of Zirconium from Sulfuric Acid Solutions at High Concentration with Trioctylamine (TOA)

Shuo Tian,Jing Song,Hongqian Sun,Congcong Zhao,Zhiyu Zhang,Mingming Han,Tao Qi

Zirconium (Zr) and hafnium (Hf) are very important in nuclear and high-temperature applications, but their similar physical and chemical properties bring great challenges to separation. The current extraction methods have defects, such as low efficiency at high metal concentration. In this article, a zirconium (Zr)/hafnium (Hf) solvent extractive separation from sulfuric acid solutions using trioctylamine (TOA) as the extractant was researched at room temperature. The aqueous solution is prepared using zirconium sulfate (containing Hf), and the concentration of metal ions (Zr4+and Hf4+) was about 1.096 mol·L−1. The effects of the aqueous acidity, the concentration of TOA, the contacting time, and the organic to aqueous O/A ratio on the separation of Zr and Hf were investigated. It is observed that the Zr can be extracted in the organic phase selectively, and the optimal conditions were: TOA concentration of 40 vol%, organic to aqueous O/A ratio of 3, contacting time of 5 min. Under these conditions, the single-stage extraction rate of Zr is 61.23%, while the Hf is almost not extracted. The mechanism of Zr extraction by TOA was studied through the saturation capacity and slope methods. Based on the results, it is believed that the structure of the extracted complex may be [R3NH]2[Zr(SO4)3]. This study provides a new approach for the development of industrialized Zr-Hf separation.

研究领域: 化学工程 · 核工业
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SEPARATION AND PURIFICATION TECHNOLOGY · 2022 · IF 9.136

Separation and extraction of niobium from H2SO4 solution containing titanium and iron impurities

Linquan Sun,Xukun Zhang,Lina Wang,Hongdong Yu,Fancheng Meng,Tao Qi,Yihe Peng

A fluoride-free solvent extraction method for niobium separation in leached sulfuric mother liquor of ilmenorutile was proposed in this paper. The extraction system comprising trioctyl tertiary amine (N235) and 4-methyl-2-pentanone (MIBK) demonstrated good extraction efficiency and selectivity of niobium over titanium and iron impurities in sulfuric acid–oxalate solutions. Details of extraction, scrubbing, and stripping processes were investigated herein, and its practical effectiveness in both batch and multi-stage simulated counter-current modes was verified. Over 73.8% niobium was extracted under optimum conditions, and only 2.8% titanium and 1.7% iron were co-extracted. The recovery of niobium reached 99.1% in the four-stage simulated counter-current extraction tests. In the three-stage simulated counter-current stripping tests, the stripping efficiency of niobium reached 99.7% with 2.0 mol/L HNO 3 . Qualified niobium oxide products were prepared. The enthalpy change, entropy change, and the standard Gibbs free energy change (Δ H o , Δ S o , and Δ G o , respectively) corroborated the exothermicity, orderliness, and spontaneity of the reaction. The possible composition of the extraction complex was [NbO(C 2 O 4 ) 2 (H 2 O) 2 ] − , as supported by a Fourier transform infrared spectroscopy and ultraviolet–visible spectrophotometry. The extraction mechanism was inferred to be the outer-sphere complexation through physical binding which was the association of R 3 NH + in N235 with the [NbO(C 2 O 4 ) 2 (H 2 O) 2 ] − . A preliminary mass balance indicated that 203.92 g Nb 2 O 5 was generated from 1000 g raw material ilmenorutile.

研究领域: 冶金学 · 化学工程
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RESEARCH ON CHEMICAL INTERMEDIATES · 2014 ·Vol. 41 ·期 10 ·7073-7093 · IF 1.54

Experimental and theoretical investigation of indole as a corrosion inhibitor for mild steel in sulfuric acid solution

Lv T. M.,Zhu S. H.,Guo L.,Zhang S. T.

The inhibiting effect of indole on the corrosion of mild steel Q235 in 0.1 M H 2 SO 4 was investigated through different approaches including weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), scanning electron microscope experiments, and theoretical calculations. Polarization curves reveal that the indole acts as a mixed-type inhibitor and the reaction mechanism in respect of either hydrogen evolution or mild steel dissolution has not been modified. EIS results imply that the water molecules adsorbed on the steel surface are substituted by the indole molecules and the inhibiting behavior of indole is probably due to the formation of an adsorptive film on the steel surface. Thus the thermodynamic and kinetic parameters are determined and discussed to give better understanding of the adsorption process. Theoretical calculations are also discussed in light of the optimized molecular structure of indole to gain further insight of the inhibition mechanism.

CAS / MDL: 120-72-9
研究领域: 材料科学 · 电化学 · 理论计算
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JOURNAL OF MOLECULAR LIQUIDS · 2022 · IF 6.633

Co-extraction of Mn2+, Co2+, and a part of Ni2+ from sulfuric acid solution containing Li+ using the new ionic liquids

Xiaohua Jing,Zhumei Sun,Dandan Zhao,Xiaoning Tang,Wenjing Lv,Yunfeng Shi

In this study, five novel ionic liquids denoted by [RNH 3 ][Cyanex 272] where R = C 4 H 9 , C 6 H 13 , C 8 H 17 , C 10 H 21, and C 12 H 25 were synthesized in a one-step reaction of straight-chain primary amines and Cyanex 272. The singe-stage extraction performance of [RNH 3 ][Cyanex 272] for the separation of Mn 2+ , Co 2+ , Ni 2+ and Li + was investigated. Compared with the other [RNH 3 ][Cyanex 272], the [C 4 H 9 NH 3 ][Cyanex 272] has good selective extraction and separation of Mn 2+ , Co 2+ , and Ni 2+ due to the smaller different value between the radius of metal ion and the radius of [C 4 H 9 NH 3 ] + . Using a three-stage cross flow extraction, the extraction percentages of Mn 2+ , Co 2+ , Ni 2+ , and Li + were about 99.4, 99.1, 14.9 and 0.9 %. The [C 4 H 9 NH 3 ][Cyanex 272] is a good extraction agent for co-extraction of Mn 2+ , Co 2+ , and a part of Ni 2+ from Li + based on a three-stage cross flow extraction. Diluted sulfuric acid was used to strip the organic phase containing Mn 2+ , Co 2+ , and Ni 2+ , and the aqueous phase containing Mn 2+ , Co 2+ , and Ni 2+ can be used for the preparation of ternary precursor materials. The precipitation method can be used to prepare Ni(OH) 2 and Li 2 CO 3 from an aqueous phase containing Ni 2+ and Li + . The conceptual recycling flow-sheet for Mn 2+ , Co 2+ , Ni 2+ , and Li + from spent ternary lithium batteries was presented on basis of the new extraction agent. The slope method was also used to investigate the mechanism of the extractive reaction of Mn 2+ , Co 2+ , and Ni 2+ using the [C 4 H 9 NH 3 ][Cyanex 272].

研究领域: 化学工程 · 材料科学
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APPLIED SURFACE SCIENCE · 2024 · IF 6.3

Pectin-derived nitrogen-doped carbon dots as green corrosion inhibitors for N80 steel in 1 M sulfuric acid solution

Yu Wu,Lingchi Zeng,Yancheng Zheng,Fuchang You,Xuejin Liu

In this study, nitrogen-doped carbon dots (N-CDs) were synthesized via a one-step hydrothermal method using pectin polysaccharide as the carbon source, with 1-hexylamine, 1,2-diaminocyclohexane, and diethylenetriamine as individual nitrogen sources. The chemical composition, fluorescence properties, and morphology of the synthesized N-CDs were characterized. Their corrosion inhibition performance on N80 steel in 1 M H 2 SO 4 was evaluated using electrochemical analyses and weight loss experiments. Tafel and EIS analyses demonstrated that at a concentration of 200 mg/L, the maximum inhibition efficiencies of PHA-CDs, PCA-CDs, and PDA-CDs, synthesized using monoamine, diamine, and triamine as nitrogen sources, were 75.3 %, 90.1 %, and 95.4 %, respectively. The inhibition efficiency increased with the total nitrogen and pyrrolic N content in the N-CDs, corresponding to the choice of nitrogen source. Weight loss experiments further confirmed these trends. Additionally, the N-CDs were found to act as mixed-type inhibitors with a predominant anodic inhibition effect and are classified as predominantly chemisorptive. The adsorption behavior adhered to the Langmuir adsorption model, where coordination complexes formed between pyrrolic N and metal Fe increase the surface coverage of the adsorption film, thereby enhancing corrosion resistance.

研究领域: 材料科学 · 电化学 · 绿色化学
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JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY · 2024 · IF 1.5

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.

研究领域: 化学工程 · 冶金学 · 环境科学
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JOM · 2022 ·Vol. 74 ·期 2 ·644-653 · IF 2.597

Facile Method for the Cadmium Separation from Zinc- and Cadmium-Bearing Dust by Zinc Plate Electroreplacement (ZPER) Process

Liu Shufen,Yang Shenghai,Wang Shuyue,Luo Tao,Chen Yongming

A novel ZPER process is proposed for Cd separation from Zn-Cd-bearing dust, where Cd was separated thoroughly from acidic leachate of the dust by zinc plate replacement with the assistance of a microcurrent, and a new reaction surface of the Zn plate could be exposed by electrodissolution, which allowed the replacement reaction to proceed continuously. First, the effects of anode current density, initial pH, and reaction temperature were investigated in detail for Zn-Cd sulfate mixed synthesis solution. Under optimum conditions, the removal ratio and residual concentration of Cd were more than 99.99%, and only 0.34 mg/L and 97.59% Cd was replaced into the anode Cd sponge, which consisted of rod-shaped and branch-like particles. The purity of the Cd sponge and the replacement mole ratio of Cd generation and Zn consumption (RMR-Zn-Cd) were 97.87% and only 1.05, respectively. Finally, similar results were obtained from a sulfuric acid leaching solution of Cd-Zn-bearing dust. The new process has the advantages of deep cadmium removal, low zinc consumption, and low production cost.

CAS / MDL: 7790-84-3 7446-20-0
研究领域: 冶金工程 · 环境科学
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY · 2022 · IF 6.76

Evaluating the synergistic effect of maple leaves extract and iodide ions on corrosion inhibition of Q235 steel in H2SO4 solution

Yue Wang,Yujie Qiang,Hui Zhi,Boyuan Ran,Dawei Zhang

In recent years, many plant extracts have been used as green corrosion inhibitors to replace traditional corrosion inhibitors, but their inhibition performance still needs to be improved. The synergistic corrosion inhibition behavior and mechanism of maple leaves extract (MLE) and potassium iodide (KI) on Q235 steel in 0.5 M H 2 SO 4 solution were firstly investigated in this work. The results demonstrate that both MLE and KI can prevent the corrosion of steel in corrosive media, and that their combined protection effect is superior. The corrosion inhibition efficiency ( η ) value reaches 93.4 % in corrosive solution with the combination of 200 mg/L MLE and 200 mg/L KI, while the maximum of η is only 81.6 % using MLE alone. In addition, Fe-N bond and Fe-O bond were found on the steel surface through the X-ray photoelectron spectroscopy (XPS) analysis, which confirm the formation of a protective film. The adsorption behavior of an inhibitory film composed of MLE and KI mixtures onto steel surface follows the Langmuir adsorption isotherm model, consisting of physisorption and chemisorption. Finally, molecular dynamics (MD) simulation indicates that inhibitor molecules can adsorb on the Fe substrate in a parallel way with high binding energy values, which supports the experiments well.

CAS / MDL: 7681-11-0
研究领域: 材料科学 · 绿色化学 · 表面化学
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CHEMICAL ENGINEERING RESEARCH & DESIGN · 2019 · IF 3.073

Amorphous porous layered-Al2O3 derived from AlFu MOFs as an adsorbent for removing fluorine ions in industrial ZnSO4 solution

Kai Yang,Yifan Li,Zejun Zhao,Zhongliang Tian,Yanqing Lai

The amorphous porous layered-Al 2 O 3 derived from aluminium fumarate metal-organic frameworks (AlFu MOFs) by roasting at 773   K under air has been applied to remove fluorine ions from industrial ZnSO 4 solution. The amorphous porous layered-Al 2 O 3 was characterized by XRD, SEM and BET. The adsorption experiments were conducted under different conditions, including adsorbent dosage, initial pH, adsorption temperature and adsorption time. And the process of removing fluorine ions is well fitted with the pseudo-second-order kinetic model and Langmuir isotherm model, which is studied by the adsorption kinetics and isotherms. The theoretical maximum adsorption capacity was 12.05   mg   g −1 . Moreover, the adsorption mechanism of the amorphous porous layered-Al 2 O 3 was analyzed by SEM-EDS and FTIR. The results indicate that the adsorption process is affected by complexation and ion exchange between fluorine ions and amorphous porous layered-Al 2 O 3 . The regeneration of the amorphous porous layered-Al 2 O 3 shows that the adsorbent could be reused to reduce the production cost.

研究领域: 材料科学 · 环境科学
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RUSSIAN JOURNAL OF APPLIED CHEMISTRY · 2022 ·Vol. 95 ·期 1 ·143-153 · IF 0.869

Extraction and Separation of Co2+ from Ni2+ Using the Novel Task-Specific Ionic Liquids of [C4H9NH3][P507]

Jing Xiaohua,Sun Zhumei,Ren Jie,Chen Jing,Pan Donghui,Chen Yufei

Abstract Novel task-specific ionic liquids of [C 4 H 9 NH 3 ][P507], [C 6 H 13 NH 3 ][P507], [C 8 H 17 NH 3 ][P507], [C 10 H 21 NH 3 ][P507] and [C 12 H 25 NH 3 ][P507] were synthesized by one-step reaction. The 1 H NMR, 13 C NMR, FT-IR and mass spectra (MS) of the novel task-specific ionic liquids s were studied for analysis of their purities. The [C 4 H 9 NH 3 ][P507] has better performance of selective separation of Co 2+ from Ni 2+ in simulated sulfate solution due to the smaller different value between the radius of Co 2+ and the radius of [C 4 H 9 NH 3 ] + . The separation factor of Co 2+ from Ni 2+ was 522 using the three-stage cross flow extraction. A cleaner separation of Co 2+ from simulated solution containing 14 and 25 g/L of Co 2+ and Ni 2+ , respectively, was achieved using this process due to the unique properties of [C 4 H 9 NH 3 ] [P507].

研究领域: 化学工程 · 环境科学
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International Journal of Electrochemical Science · 2023 · IF 1.5

Electrochemical and Theoretical Study of Corrosion Inhibition on X60 Steel in H2SO4 Solution by Omeprazole

Yanxia Liu,Wei Du,Xiuquan Yao,Chunlin Liu,Xiaofang Luo,Lei Guo,Chao Guo

The corrosion inhibition performance of Omeprazole (OMP) on X60 steel in 0.5M H 2 SO 4 solution was studied by electrochemical impedance spectroscopy and electrochemical polarization curves. These tests are complemented by theoretical calculations using molecular dynamics. The corrosion inhibition efficiency increases with the concentration of OMP, a hybrid corrosion inhibitor that adsorbs on X60 steel following the Langmuir adsorption isotherm. The adsorption configuration calculated by molecular dynamics showed that the OMP molecules were arranged in parallel on the surface of X60 steel, which ensured its excellent inhibition performance.

CAS / MDL: 73590-58-6
研究领域: 材料科学 · 电化学 · 理论计算
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2018 · IF 3.141

Optimal Design of Neutralization Process in 1,5-Dihydroxynaphthalene Production with Solubility Difference of Naphthalene-1,5-disulfonic Acid and Naphthalene-1,5-disulfonic Acid Disodium in Aqueous Sulfuric Acid Solutions

Yong-Sheng Xu,Rui-Xiong Zhao,Kang-Kang Pei,Guo-Liang Zhang,Qing Xia,Feng-Bao Zhang

An optimal design of the neutralization process in 1,5-dihydroxynaphthalene production was proposed and discussed. In the new strategy, instead of sodium chloride, sodium sulfate was used in the salting-out process to overcome the drawbacks of the traditional strategy. Then the precipitated mixtures, mainly naphthalene-1,5-disulfonic acid (1,5-H2NDS) and sodium sulfate, were neutralized to obtain naphthalene-1,5-disulfonic acid disodium (1,5-Na2NDS) and sulfuric acid. By adjusting the concentrations of sulfuric acid solutions to 0.3 and 0.5 mass fractions, 1,5-Na2NDS and 1,5-H2NDS were precipitated out, respectively. The yields of both 1,5-H2NDS and 1,5-Na2NDS reached 0.98. 1,5-Na2NDS was sent to the alkali fusion process, while 1,5-H2NDS was reused in the neutralization. In neutralization, the mole ratio (1,5-H2NDS to sodium sulfate) was chosen as 2.5 and the reaction temperature was 353 K. In order to determine the separation conditions, the solubilities of 1,5-H2NDS·2H2O and 1,5-Na2NDS·H2O in aqueous sulfuric acid solutions were measured over the temperature range from 277 to 337 K at atmospheric pressure by a dynamic method. The new strategy is particularly instructive for the industrial production of 1,5-dihydroxynaphthalene.

CAS / MDL: 7757-82-6
研究领域: 化学工程 · 工业化学
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