Arabian Journal of Chemistry
·
2023
·
IF 6
Hongru Zhao,Chengqiang Hu,Na Sui,Xinyu Liu,Junlian Wang
Zr/Hf separation has always been a great challenge. Although the methyl isobutyl ketone (MIBK)-thiocyanic acid (HSCN) extraction system selectively extracts Hf over Zr and can realize Zr/Hf separation, it has the following disadvantages: it has a strong smell; it is easy to burn; and there is large loss of extractant during extraction due to the low boiling point (115.7 °C), low flashing point (13 °C), and high solubility of MIBK in water (1.7 % at 25 °C). In this study, Zr/Hf separation performance by MIBK homologues — of which one side of C = O is iso pentyl, iso hexyl, n -pentyl, n -hexyl or n -heptyl, while the other side are all methyl — were studied and compared with MIBK. Effects of HSCN pre-extraction, HCl concentration, NH 4 SCN concentration on Zr, Hf extraction and separation performance were investigated. Relationships between methyl alkyl ketone structure and their Zr/Hf separation performance were revealed. A new Zr/Hf separation system MNPK (methyl n -pentyl ketone)-HSCN was found. MNPK has a higher boiling point (151 °C), a higher flashing point (47 °C) and a lower solubility in water (0.43 % at 20 °C) than MIBK. Compared to MIBK, it is safer, more friendly operation environments and less extractant loss during extraction. MNPK has as fast extraction kinetics as MIBK. It also has good anti-emulsification performance. Its maximum β Hf/Zr can reach to 12.61. The loaded Zr and Hf in MNPK have very similar stripping behaviors with those loaded in MIBK by HCl and H 2 SO 4 solutions, respectively. MNPK is the most possible candidate to replace MIBK from HSCN media in Zr/Hf separation industry.
研究领域:
化学工程
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材料科学
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DOI
高影响因子
HYDROMETALLURGY
·
2021
·
IF 4.156
Linquan Sun,Hongdong Yu,Fancheng Meng,Tao Qi,Shili Zheng,Yihe Peng,Lina Wang
Niobium consumption has burgeoned owing to the increasing application of niobium in critical industries, including the aerospace and oil and gas industries. Conventional metallurgical technologies and separation methods for niobium extraction use highly concentrated HF, which is hazardous to both humans and the environment. A solvent extraction system comprising trioctyl tertiary amine (N235) and 4-methyl-2-pentanone (MIBK) that can extract and separate niobium from an oxalate-containing H 2 SO 4 solution is proposed in this paper. Niobium solutions tend to contain titanium and iron impurities; therefore, the effects of various conditions on the separation of the three elements were investigated. The extraction mechanism and thermodynamics of the process were also examined. Over 82% niobium was extracted at an organic-to-aqueous phase ratio of 1:1 and the H + concentration of 8.29 mol/L using an organic phase with 50 vol% N235 and 50 vol% MIBK as the extractants at 20 °C. Only 18.4% titanium and 3.35% iron were co-extracted. Two stripping processes, both of which further separated niobium and titanium, are also proposed herein. The possible composition of the niobium-containing extraction complex was [(R 3 NH)·NbO(C 2 O 4 ) 2 (H 2 O) 2 ], as supported by a Fourier transform infrared spectroscopy (FT-IR) analysis and ultraviolet–visible (UV–vis) spectrophotometry . The extraction mechanism was inferred to be the association of R 3 NH + in N235 with the [NbO(C 2 O 4 ) 2 (H 2 O) 2 ] − from the acidic niobium-containing solution, and the stripping mechanism was concluded to be anion exchange. The enthalpy change (∆H o ) of the extraction system was −11.0 kJ/mol at 288.15–313.15 K, which indicated that niobium extraction from the H 2 SO 4 solution with oxalate using N235 and MIBK was an irreversible exothermic process.
研究领域:
冶金学
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化学工程
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DOI
高影响因子
DESALINATION
·
2024
·
IF 8.3
Li Wang,Jianfeng Zhang,Shixin Meng,Huiyong Wu,Yunze Zhao,Zhen Meng,Lei Feng,Huanting Wang,Yuan Cheng,Liangrong Yang,Huizhou Liu
The dissolution loss of extractant into aqueous solution during lithium solvent extraction from salt lakes poses a significant issue. We found that branched chains of neutral organophosphorus extractants provide suitable steric hindrance, enhancing lithium extraction efficiency and Li/Mg selectivity. Additionally, increasing the number of alkyl chains in organophosphorus extractants increases their hydrophobicity, thereby reducing extractant dissolution loss during the extraction process. Based on these findings, a novel extraction system comprising tri(2-ethylhexyl) phosphate (TOP), FeCl 3 , and 4-methyl-2-pentanone (MIBK) was explored. The extraction conditions, including the Fe/Li molar ratio, diluents, phase ratio, and stripping conditions, were thoroughly investigated and optimized. The extraction mechanism was elucidated at the molecular level using FT-IR, Raman, NMR, and density functional theory (DFT) calculations. The results demonstrated that the TOP-FeCl 3 -MIBK system achieved an 85 % extraction efficiency for Li + in a single stage, with a Li + /Mg 2+ separation factor reaching 5842, surpassing previously reported data in the literature. 31 P NMR and 7 Li NMR analyses revealed that the TOP and tributyl phosphate (TBP) complexes existed in different forms within the organic phase. Slope analysis indicated that the stoichiometric ratio of the extraction complex involving Li + , TOP, and MIBK was LiFeCl 4 ·TOP·MIBK. Furthermore, DFT calculations indicated that the TOP complex was more stable than the TBP complex after extraction. We anticipate that our findings will pave the way for the development of a series of novel extractants with higher Li/Mg selectivity by enhancing steric hindrance and incorporating longer alkyl chains to minimize dissolution loss. We expect this research to inspire the development of similar neutral organophosphorus extractants.
研究领域:
化学工程
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材料科学
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产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
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2024
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IF 5.3
Erkang Li,Yujie Zhen,Lu Chen,Xuqiang Li,Lei Li,Wenxue Lu,Tao Li,Qingsong Li,Yingmin Yu
Pyridine compounds play a crucial role in the synthesis of fine chemicals and pharmaceuticals; however, the generation of a large amount of wastewater may pose a threat to the ecological environment and human health. Considering environmental factors and economic benefits, it is essential to explore efficient methods for separating pyridine compounds from water. In this study, pyridine compounds were separated from water by liquid–liquid extraction using MIBK as solvent. Liquid-liquid equilibrium (LLE) data for the ternary system water + pyridine compounds(pyridine, 2-methylpyridine, 3-methylpyridine, 2,6-dimethylpyridine, and 2,4,6-trimethylpyridine) + MIBK were measured at 303.2 K and 101.3 kPa. Subsequently, the distribution coefficient ( D ) and separation factor ( S ) were calculated based on the obtained data, serving as indicators to evaluate the performance of the extractant. The LLE data were then correlated with NRTL and UNIQUAC models to obtain binary interaction parameters. The accuracy of the regressed binary interaction parameters was assessed through Gibbs energy topology analysis. To explore the intrinsic mechanism of extraction between MIBK and pyridine or alkylpyridines, the σ-profile was used to investigate the interaction form between MIBK and pyridine or alkylpyridines. Based on this, quantum chemical calculations and wave function analysis were used to reveal the molecular-level separation mechanism. The interaction behavior of the MIBK and pyridine or alkylpyridines systems was systematically investigated. The results indicate that van der Waals forces are the main intermolecular interactions , and it is through these strong forces that MIBK can efficiently separate pyridine and alkylpyridines from water.
研究领域:
环境科学
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物理化学
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DOI
高影响因子
Reaction Kinetics Mechanisms and Catalysis
·
2022
·Vol. 135
·期 4
·1957-1970
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IF 1.843
Wang Chengqian,Zhao Caiyi,Zhang Long
To enhance the selective fructose dehydration to 5-hydroxymethylfurfural (HMF), an efficient dehydration of fructose to 5-HMF in H 2 O-MIBK- pressured CO 2 in 20 min at 200 °C with a better product yield of 85.6% and 89.1% product selectivity was achieved. The high activity attributed to the combination of the weak acidity by CO 2 dissolved in the water and the efficient separation of fructose with 5-HMF in this H 2 O-MIBK two-phase system. The possible reaction mechanism is discussed. It was found that the solvents ratio was the one of key factors determining the yield of target products. Compared to the related reported results in the reaction, this process characterized of more favorable product yield and higher selectivity, it can be considered as a potential technique for the scale-up production of 5-HMF from fructose.
研究领域:
化学工程
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催化
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绿色化学
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DOI
高影响因子
RSC Advances
·
2020
·Vol. 11
·期 1
·48-56
·
IF 3.119
Yingjie Hu,Yuxin Mei,Baining Lin,Xuhong Du,Fan Xu,Huasheng Xie,Kang Wang,Yonghua Zhou
The one-pot synthesis of methyl isobutyl ketone (MIBK) and methyl isobutyl methanol (MIBC) from acetone and hydrogen is a typical cascade reaction comprised of aldol condensation-dehydration-hydrogenation. Pd loss and aggregation during long term operation are typical problems in industrial application. In this paper, an active and stable catalyst was achieved with defective UiO-66 as a support for Pd, which was synthesized with the ratio 15 : 1 of ZrOCl2·8H2O to ZrCl4 as Zr-precursors. The resultant Pd catalyst remained active for at least 1000 h with a MIBK + MIBC selectivity of 84.87–93.09% and acetone conversion of 45.26–53.22% in a continuous trickle-bed reactor. Besides the increased Brønsted acid amount generated by the defect sites was favorable for the activity, the cavity confinement in the UiO-66 (R = 15 : 1) structure also efficiently prevented Pd loss and aggregation during the long term run. The contrast of the characterization of the fresh and used Pd/UiO-66 (R = 15 : 1) indicated that the deactivation of the catalyst was attributed to carbonaceous accumulation on the catalyst surface, which could be easily regenerated by calcination. This work supplied a new alternative for the design and utilization of industrial catalysts for MIBK and MIBC synthesis.
研究领域:
催化化学
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材料科学
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产品关联
DOI
PubMed
高影响因子
Journal of Cleaner Production
·
2018
·
IF 5.651
Chao Guo,Qi Cao,Bokun Chen,Siyu Yang,Yu Qian
Due to the limitation of the existing solvents, the phenols recovery process cannot control phenols concentration to less than 300 mg/L. Therefore, this study presented a synergistic phenols extraction process by using optimal design solvent mixture. The solvent mixture was proposed with the volume ratio of methyl isobutyl ketone (MIBK) to n-pentanol 6:4. The synergistic extraction process was simulated to acquire the parameters with treatment 130 t/h coal gasification wastewater. The removal efficiencies of phenols and treatment costs for the synergistic extraction process had been addressed. The removal efficiency of total phenols can reach to 97.0% after two-stage extraction, and the concentration of total phenols can be decreased from 6273 mg/L to 190 mg/L. Compared with single solvent MIBK, the reduction of phenols emissions is 47.2% by proposed solvent mixture. The operation cost and income of crude phenols showed that synergistic extraction process realized profit about 3.35 CNY/t. Given the removal efficiencies and treatment costs, the solvent mixture (60% MIBK, 40% n-pentanol) is very promising for phenols removal.
研究领域:
环境科学
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化学工程
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2026
·
IF 9.1
Rui Qin,Ji Chen,Yuefeng Deng,Shuang Sun,Biyou Zhang
Recognized as a critical element, lithium underpins the advancement of renewable energy and nuclear technologies. Most lithium reserves in China are distributed in the salt lake brines of the Qinghai and Tibet regions. However, the formidable technical challenges associated with recovering lithium from salt lakes have limited their development and utilization, particularly for salt lakes with a high Mg/Li ratio. Traditional extraction systems often suffer from drawbacks, including low extraction efficiency, high water solubility, and poor economic feasibility. In this study, an innovative and efficient extraction system (DEHEHP-MIBK) was proposed for recovering lithium via countercurrent extraction from brines with a high Mg/Li ratio. The optimal parameters, including extractant concentration, Fe/Li molar ratio, brine pH, equilibrium time, and O/A phase ratio, were determined. Through 6-stage countercurrent extraction, 99.9% of lithium was extracted from the brine. Subsequently, the scrubbing and stripping conditions were investigated, yielding a stripping solution with a lithium content of 22.56 g/L and a Mg/Li ratio reduced to 0.002. The 98.9% purity lithium carbonate (Li 2 CO 3 ) products were fabricated through precipitation from the stripping liquor. The intrinsic mechanism of lithium extraction in the DEHEHP-MIBK system was probed using a slope analysis method and Fourier transform infrared (FT-IR) spectroscopy. It can be inferred from the results that the composition of the extracted compound is LiFeCl₄·DEHEHP·MIBK. Density functional theory (DFT) computations further explain the superior performance of this system in depth. This study provides an efficient method that offers novel insights into the selective recovery of lithium from high Mg/Li ratio salt lakes.
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DOI
高影响因子
Polymers
·
2020
·Vol. 12
·期 2
·378
·
IF 3.426
Qilin Zhang,Haichao Li,Zongwei Guo,Feng Xu
A simple and economical biorefinery method, organosolv methyl isobutyl ketone (MIBK) pretreatment assisted by Lewis acid ferric trichloride hydrolysis, was proposed for fractionating the lignin from extractive-freeEucalyptuspowder at the nanoscale, accompanied by another product furfural, derived from hemicellulose. Under the conditions (180 °C, 1 h) optimized based on the best yield of furfural, 40.13% of the acid-insoluble lignin (AIL) could be obtained with a high purity of 100%, a low molecular weight of 767 (Mn) and improved thermostability. The extracted lignin was characterized by its chemical structure, thermostability, homogeneity, molecular weight, and morphology as compared with milled wood lignin (MWL). The results showed significant variations in chemical structures of the extracted lignin during the pretreatment. Specifically, the aryl ether linkage and phenylcoumarans were broken severely while the resinols were more resistant. The G-type lignin was more sensitive to degradation than the S-type, and after the pretreatment, H-type lignin was formed, indicating the occurrence of a demethoxylation reaction at high temperature. Moreover, the lignin nano-particles were identified visually by AFM and TEM images. The dynamic light scattering (DLS) showed that the average diameter of the measured samples was 131.8 nm, with the polydispersity index (PDI) of 0.149. The MIBK-lignin nano-particles prepared in our laboratory exhibit high potentials in producing high functional and valuable materials for the application in wide fields.Keywords:lignin nano-particles;organosolv pretreatment;Eucalyptuswood;biomass;biorefinery
研究领域:
化学工程
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材料科学
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生物质技术
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生物技术
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产品关联
DOI
PubMed
高影响因子
HYDROMETALLURGY
·
2026
·
IF 6.3
Gengjin Zhang,Yanfang Huang,Longfei Jia,Tianze Chen,Yizhuang Wang,Shengpeng Su,Wenjuan Wang,Hu Sun,Guihong Han
Novel peroxo-complexation strategy was used to purify Nb-rich solution. • NbOF 5 2− transformation to NbO 2 F 5 2− greatly lowers its binding energy with MIBK. • Selectivity coefficient for Sb over Nb was enlarged by over 2300 times. • Nb 2 O 5 product met the high-purity specifications regarding Ta and Sb impurities. The efficient separation of Ta and Sb from Nb in hydrometallurgical processes remains a significant challenge due to their similar chemical behaviors. In this study, a novel peroxo-complexation strategy was introduced to enhance the selectivity of methyl isobutyl ketone (MIBK) extraction in an HF-H 2 SO 4 system. With the addition of H 2 O 2 , the extraction efficiencies of Ta and Sb reached 99.6% and 99.7%, respectively, while the co-extraction of Nb was only 2.32%. The selectivity coefficients of Sb/Nb and Ta/Nb significantly increased from 0.63 and 34.7 to 1461 and 6501, respectively. Stepwise stripping using H 2 SO 4 and pure water effectively recovered Nb and Ta/Sb from the loaded organic phase. Raman spectroscopy and quantum chemical calculations elucidated the mechanism of the enhanced separation selectivity. The peroxo-ligand selectively coordinates with Nb to transform it from NbOF 5 2− to NbO 2 F 5 2− , thereby weakening the negative surface potential of the fluorine atoms bonded to Nb. The binding energy between Nb ions and MIBK decreases from −172 kJ mol −1 to −104 kJ mol −1 , and thus the disparity in the affinity of Nb ions and Ta/Sb ions for MIBK is magnified. Overall, this peroxo-coordination approach provides an efficient and simple pathway for the effective purification of Nb solutions. Download: Download high-res image (176KB) Download: Download full-size image
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DOI
高影响因子
Journal of Physical Chemistry C
·
2022
·
IF 4.177
Lin Chai,Hongliang Wang,Hongyan Li,Lijuan Su,Shiyu Jia,Xiaojie Shao,Yingxiong Wang,Yongqin Qi,Xiaojing Cui,Xianglin Hou,Tiansheng Deng
The common method for producing graphene, the oxidation and reduction method, is not green due to application of corrosive oxidants and reductants, and the obtained graphene is rich in surface defects. Here, we show a novel edge-decoration strategy for the facile exfoliation of graphene layers from graphite. By grafting methyl isopropyl ketone (MIBK) onto the edges of graphite via the aldol condensation reaction, the dense graphene layers become loose, facilitating the exfoliation process and promoting largely the graphene yield from 1.6 to 10.9 wt %. The edge-decoration strategy produces graphene with 5–10 layers and few surface defects. Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and activation experiments prove that the edges of graphite reacted with MIBK via C═O as the active site, causing the grafting of MIBK. We anticipate that the edge-decoration strategy will show great potential in the large-scale production of graphene due to its high efficiency and greenness.
研究领域:
材料科学
·
化学
·
纳米技术
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Zhouxuan Zang,Jianhua Zhou,Ningke Pang,Wencai Bai,Yong Xiang,Yi Yu,Li Xu,Guoji Liu
High-energy-density sustainable aviation fuels are recognized as effective means to mitigate carbon emissions in the aviation sector. Here, we report various metal-modified layered double hydroxides (LDHs). The screened MgAlSn-LDH catalyst incorporating abundant oxygen vacancies and strong base sites yields (E)-1-(furan-2-yl)-5-methylhex-1-en-3-one (ALD) over 96% at 120 °C for 4 h. The catalyst exhibits promising long-term stability in a fixed-bed reactor at 170 °C. A combination of investigations using in situ DRIFTS studies and DFT calculations reveals that MgAlSn-LDH enhances the adsorption of methyl isobutyl ketone (MIBK) and furfural (FF). Further calculations have shown that the synergy of oxygen vacancies and strong base sites decreases the energy barrier of MIBK enolation, which increases the rate of the enolation reaction. This research provides a versatile synthesis method for improving the alkaline catalytic activity of LDH catalysts, and the performance of the catalysts can be extended to other upgrading processes of biomass chemicals.
研究领域:
催化
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材料科学
·
化学工程
·
可再生能源
·
表面化学
·
计算化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）