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SEPARATION AND PURIFICATION TECHNOLOGY · 2021 · IF 7.312

Development of a reactive extraction process for enhancing acetalizations of ethylene glycol and 1,2-butanediol with propyl aldehyde

Rui Wang,Jian Na,Xingang Li,Hong Li,Sai Gu,Xin Gao

Ethylene glycol (EG) is a widely used industrial chemical material, and integrated chemical-looping separation technology (CLS) was verified effective to remove 1,2-butanediol (1,2-BDO) and recover EG produced via the syngas to EG route. Thermodynamic experiments were carried out and employed to analyze the vapor–liquid and liquid–liquid behaviors of the system. Propyl aldehyde, apart from as the reactant, also shows excellent performance in water removal and acetals extraction. Based on the results of the thermodynamic analysis, a reactive extraction process was proposed to intensify the acetalization of EG and 1,2-BDO mixture with propyl aldehyde. The reactive extraction model was established on Aspen Plus v11, and the effects of flow mode (co-current and counter-current), number of stages, the feed-in mole ratio of aldehyde to DIOL on the conversions of EG and 1,2-BDO, the recovery of 2-ethyl-1,3-dioxolane (2ED), and the purity of acetals were investigated. Results show that co-current flow mode performs better than counter-current flow mode and an aldehyde to DIOL feed-in mole ratio of 1.35 to 1 is sufficient. The whole flowsheet, which consists of a seven-stage reactive extraction column and two distillation columns, was designed and optimized. Remarkably, the conversions of EG and 1,2-BDO are over 0.95 and the recovery of 2ED is 0.999 with the aldehyde to DIOL stoichiometric coefficient, which indicates the effectiveness of this process and provides fundamental data and guidance for industrial application.

CAS / MDL: 67-68-5
研究领域: 化学工程 · 工业化学
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CATALYSIS TODAY · 2019 · IF 4.888

Ionic liquid [BMIm][HSO4] as dual catalyst-solvent for the esterification of hexanoic acid with n-butanol

Qian Zeng,Zhen Song,Hao Qin,Hongye Cheng,Lifang Chen,Ming Pan,Yi Heng,Zhiwen Qi

Butyl hexanoate (BuHE) is currently synthesized through the Fischer esterification with mineral acid as catalyst, which suffers from the problems of side reaction, difficult recycling, and corrosion. To overcome these disadvantages, ionic liquid 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIm][HSO 4 ]) is employed as dual catalyst-solvent for the esterification of hexanoic acid (HeAc) with n-butanol (BuOH) in a reactive extraction process. The dual functions of [BMIm][HSO 4 ], extraction and catalysis, were confirmed by liquid-liquid equilibria for the two systems {[BMIm][HSO 4 ] + HeAc + BuHE} and {[BMIm][HSO 4 ] + BuOH + BuHE}, and by the comparison of esterifications with or without [BMIm][HSO 4 ], respectively. Moreover, the optimal reactive extraction conditions for BuHE formation were obtained. Finally, the possible mechanism of intensification of [BMIm][HSO 4 ] on BuHE formation in reactive extraction process was proposed.

CAS / MDL: 71-36-3 142-62-1
研究领域: 化学工程 · 催化科学
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KOREAN JOURNAL OF CHEMICAL ENGINEERING · 2018 ·Vol. 35 ·期 6 ·1312-1318 · IF 2.199

Efficient conversion of fructose to 5-[(formyloxy)methyl]furfural by reactive extraction and in-situ esterification

Xiong Caixia,Sun Yong,Du Juan,Chen Wei,Si Zhihao,Gao He,Tang Xing,Zeng Xianhai

5-[(Formyloxy)methyl]furfural (FMF), an analogue of 5-(hydroxymethyl)furfural (HMF) is becoming more attractive due to its superior stability and hydrophobicity, which make it easier to refineand store. In the present study, FMF was produced from fructose by one-pot approach in pure formic acid media or by a two-step approach via HMF in choline chloride (ChCl)/fructose deep eutectic solvents (DES) system. A favorable FMF yield of 63.22% was reached by two-step approach. In addition, the effects of reaction parameters, such as temperature and acidity, on preparation of FMF from fructose were systematically investigated. The dehydration of fructose into HMF was confirmed as the rate-controlling step in the consecutive reaction. Ultimately, the separation and purification procedures of FMF were put forward. The FMF with a purity of 98.8% was obtained finally. Meanwhile, the FMF purified by saturated sodium bicarbonate solution showed an excelled storage stability.

研究领域: 化学工程 · 生物化工
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AICHE JOURNAL · 2021 ·Vol. 67 ·期 8 ·e17252 · IF 3.993

Performance and mechanism of the separation of C8 α-olefin from F-T synthesis products using novel Ag-DES

Hu Li,Zisheng Zhang,Guanlun Sun,Suli Liu,Liangcheng An,Xingang Li,Hong Li,Xin Gao

As an attractive alternative technology for the separation of long chain olefin and paraffin, a novel silver-based deep eutectic solvent (Ag-DES) was prepared and utilized for 1-octene/n-octane separations. Comprehensive reactive extraction separation experiments were performed to highlight the Ag-DES concentration and operating temperature discriminations using compounds with different ratio of 1-octene/n-octane. The novel Ag-DES showed optimal separation performance regarding 1-octene/n-octane and possessed the highest levels separation selectivity in the range 3.57–16.11 with excellent circulation stability in our best knowledge. Furthermore, FT-Raman measurements and quantum chemistry calculation were performed to elucidate the interaction mechanism of Ag-DES in the separation of 1-octene and n-octane, which revealed that both chemical complexation and strong physical attraction existed in the complex of Ag-DES and 1-octene rather than n-octane. A practical process was proposed for the separation of olefin and paraffin, which indicates that an advanced separation technology could largely reduce the energy consumption. This study lends important insight for the development of Ag-DES reactive extraction separation process for the energy-efficient long chain α-olefins purification from F-T synthesis products.

CAS / MDL: 611-74-5
研究领域: 化学工程 · 能源科学
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Advanced Science · 2024 · IF 14.3

Tailoring Type III Porous Ionic Liquids for Enhanced Liquid-Liquid Two-Phase Catalysis

Peiwen Wu,Bangzhu Wang,Linlin Chen,Jie Zhu,Ning Yang,Linhua Zhu,Chang Deng,Mingqing Hua,Wenshuai Zhu,Chunming Xu

Porous Ionic Liquids (PILs) have gained attention but facing challenges in catalysis, especially in liquid-liquid two-phase reactions due to limited catalytic sites and hydrophilicity control. This work engineered a Type III PILs (PILS-M) using zeolitic imidazolate framework-8 (ZIF-8) confined phosphomolybdic acid (HPMo) as the microporous framework and N-butyl pyridine bis(trifluoromethane sulfonyl) imide ionic liquid ([Bpy][NTf 2 ]) as the solvent. The PILS-M not only combines the advantages of traditional ionic liquids and microporous frameworks, including excellent extraction, high dispersion of catalytically active species, remarkable stability, etc ., but also can make the inner surface of ZIF-8 turned to be hydrophilic that favors the contact between aqueous hydrogen peroxide oxidant and catalytically active sites for the promotion of catalytic performance in reactive extractive desulfurization (REDS) processes of fuel oils. This study demonstrates Type III PILs' potential as catalysts for sustainable chemical processes, offering insights into versatile PILs applications in diverse fields.

研究领域: 化学工程 · 催化材料
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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2020 · IF 2.627

Reactive extraction for synthesizing long chain ester butyl hexanoate intensified by deep eutectic solvent

Yishan Zhou,Hao Qin,Hongye Cheng,Lifang Chen,Bingjian Zhang,Zhiwen Qi

Butyl hexanoate (BuHE) is an important long-chain ester that is widely used in the food, beverage and cosmetic industries. In this work, reactive extraction concept was proposed to intensify the BuHE formation in a biphasic system, in which deep eutectic solvent (DES) comprising 2-methylimidazole (2-MIm) and p -toluenesulfonic acid (PTSA) was used as dual solvent-catalyst. First, the effect of 2-MIm to PTSA molar ratio on esterification was investigated to determine the optimum DES of [2-MIm:2PTSA], which was characterized by FT-IR and TGA. Then, the liquid–liquid equilibrium (LLE) and esterification experiments were carried out to confirm the extraction and catalytic effect of [2-MIm:2PTSA], respectively. Afterwards, the pseudo-homogeneous kinetic model was employed to describe the esterification kinetics. Finally, the intensification mechanism of reactive extraction for BuHE formation was proposed according to the experiments and interaction effect analysis.

研究领域: 化学工程 · 有机合成
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GREEN CHEMISTRY · 2014 ·Vol. 16 ·期 11 ·4669-4679 · IF 6.852

Etherification of glycerol with isobutene on sulfonated graphene: reaction and separation

Jinxia Zhou,Yu Wang,Xinwen Guo,Jingbo Mao,Shuguang Zhang

A sulfonated graphene catalyst (SG) prepared by grafting sulfonic acid-containing aryl radicals onto the two-dimensional surface of graphene was used for the etherification of glycerol with isobutene, and a reaction–extraction process was developed for easy realization of product isolation and catalyst recycling. With its ultra thin two-dimensional open substrate, stable sulfonic acid sites, amphiphilic properties and light texture, SG exhibited excellent catalytic performance in the etherification reaction. At 60–70 °C with 4 wt% catalyst loading and a molar ratio of isobutene/glycerol 4, a nearly complete conversion of glycerol in 7 h and a selectivity of more than 90 mol% to desired multi-butyl glycerol ethers were achieved. Moreover, undesired oligomerization of isobutene was successfully suppressed. When extracted with fresh glycerol, the mixture after reaction was successfully layered to two phases, with a transparent liquid containing no less than 96 wt% di- and tri-butyl glycerol ethers in the top phase as a product and a black mixture consisting of glycerol and SG in the bottom phase which can be used to start a new run with fresh isobutene addition. During six consecutive reaction–extraction cycles the catalyst maintained its robust performance.

CAS / MDL: 1314-56-3
研究领域: 化学工程 · 催化科学
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Intensified direct synthesis of dimethyl carbonate from CO2 using 1-alkyl-3-methylimidazolium triazolide ionic liquids by reactive extraction strategy

Jiawei Ruan,Xiaoyi Zhang,Wanting Zhang,Xinzi Wu,Qian Liu,Zhen Song,Lifang Chen,Zhiwen Qi

The direct synthesis of dimethyl carbonate (DMC) from CO 2 is a promising route for CO 2 utilization, however it is constrained by high CO 2 activation barrier and inherent thermodynamic limitations. Herein, we developed a reactive extraction strategy to intensify the reaction through 1-alkyl-3-methylimidazolium triazolide ionic liquids (ILs) (CnMImTz, n = 2, 4, 6, and 8) by modulating IL polarity. The absorption and activation mechanism of CO 2 in ILs was demonstrated, and subsequent transformation into DMC can be achieved under mild conditions. Remarkably, C2MImTz achieves the highest DMC yield (9.4 % after 12 h at 25 °C), revealing chain-length dependent catalytic efficiency of IL analogs at both kinetics- and thermodynamic-controlled stages. Phase analyses, binding energy calculations, and molecular dynamics simulations revealed that the highly polar C2MImTz preferentially concentrate CH 3 OH and H 2 O, while spontaneously segregating weakly polar DMC into a separate phase. The enhanced CH 3 OH concentration and diffusion coefficients promote the mass transfer and reaction kinetics. Moreover, the segregation of DMC can effectively shift thermodynamic equilibrium toward DMC formation. Therefore, the integrated absorption-conversion-separation process within a single functionalized IL presents a scalable platform for CO 2 capture and utilization.

研究领域: 化学工程 · 环境科学 · 材料科学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2025 · IF 9

Efficient synthesis of LiFSI based on Reaction-Extraction coupling method

Shouquan Zhou,Yan Liu,Fengjiao Ren,Siyu Zhang,Xueying Shi,Bin Wu,Longfei Yan,Jingjing Chen,Fuweng Zhang

Lithium bis(fluorosulfonyl)imide (LiFSI) is a promising electrolyte for lithium-ion batteries. However, the lithiation reaction during the LiFSI synthesis process is accompanied by a LiFSI hydrolysis reaction, which negatively affects the LiFSI yield and poses potential safety risks. In this study, we delve into the reaction equilibrium and hydrolysis behavior during the lithiation reaction and identify that the high temperature and strong alkali used in the reactive distillation process are the key factors leading to LiFSI hydrolysis. As a solution, a novel method for effectively synthesizing LiFSI using reaction-extraction coupling method is proposed and rigorously tested for various factors, including temperature, alkali equivalent, type of solvent, and dosage. The research culminated in developing a multistage continuous membrane extraction process, which achieves a remarkable conversion of over 99.7% and minimizes LiFSI hydrolysis to less than 0.05%.

CAS / MDL: 1310-66-3 121-44-8
研究领域: 化学工程 · 材料科学
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Chemical Engineering and Processing-Process Intensification · 2018 · IF 2.826

Process optimization of reactive extraction of clorprenaline enantiomers by experiment and simulation

Wanru Wang,Weifeng Xu,Guilin Dai,Panliang Zhang,Kewen Tang

This paper studied the process optimization of reactive extraction of clorprenaline enantiomers (CP) by experiment and simulation. An efficient extraction system was obtained through single stage extraction experiments, where boric acid (BA) in aqueous phase and D -isobutyl tartrate (DT) in organic phase were selected as extractant and 1,2-dichlorethane was selected as organic solvent. The best enantioselectivity (α) with 2.012 was obtained. The extraction mechanism was proposed and thermodynamic constants such as physical partition coefficient and reactive equilibrium constants were obtained. Based on single stage extraction, phase and reactive equilibrium as well as the law of mass conservation, a model describing the fractional extraction process was acquired. The process of symmetrical separation of CP was optimized by the model. The optimal conditions including flow rate ratio (O/W) of 1.5, pH of 5.0, CH 3 COONa/CH 3 COOH solution of 0.1 mol/L, clorprenaline concentration of 5 mmol/L, BA concentration of 0.10 mol/L and DT concentration of 0.075 mol/L were obtained. Under this case, equal enantiomeric excess (ee eq ) could reach up to 67% by 10 stages. The simulated results revealed that the minimum series for ee eq > 97% and ee eq > 99% were 26 and 33, respectively. The results will provide guides for scale up and design.

CAS / MDL: 147-71-7 87-69-4
研究领域: 化学工程 · 制药工程
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JOURNAL OF CHROMATOGRAPHY A · 2018 · IF 3.716

Development of an analytical method for urocanic acid isomers in fish based on reactive extraction cleanup and chaotropic chromatography techniques

Jian-Jun Zhong,Ningbo Liao,Mingfeng He,Yunfeng Pu,Donghong Liu

Urocanic acid (UA), existing in trans - or cis -isoform, is of fairly recent interest to food researchers because of its potential public health hazards of scombrotoxicity and immunotoxicity, as well as associating with fish spoilage. This work is among the first efforts to study the analytical chemistry of UA in fish. With 0.6 M perchloric acid UA was extracted, and co-extracted fish matrix components were efficiently removed through a reactive extraction of UA. The optimum conditions for the reactive extraction, which allowed an 80% recovery of UA, were sample pH adjustment to 9, twice extractions with 32% (w/w) di (2-ethylhexyl) phosphate in hexanol, and a back-extraction with 0.1 M hydrochloric acid at 1:1 phase ratio. A chaotropic hexafluorophosphate salt was added to acidic water-acetonitrile mobile phases to improve the reversed-phase chromatography of UA, which otherwise was poorly retained. Optimum separation conditions were obtained for fish samples and enabled a fast (10 min), convenient-to-use chromatography that clearly outperforms cumbersome legacy ion-pair chromatography. Intended for routine use in our laboratory, the proposed method passed an in-house validation test for linearity, matrix effect (on reactive extraction), accuracy, precision, and detectability.

研究领域: 分析化学 · 食品科学 · 毒理学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2020 · IF 5.774

Efficient recovery of bio-based 1,2,4-butanetriol by using boronic acid anionic reactive extraction

Qiyu Meng,Jiemiao Yu,Liangrong Yang,Yanqing Li,Mo Xian,Huizhou Liu

Effective isolation of 1,2,4-butanetriol (BT) from the fermentation broth with low BT concentration was achieved based on anionic reactive extraction with a combined extractant consisted of boronic acid carrier and trioctylmetylammonium Aliquat® 336 (A336) dissolved in the organic phase. The influence of various diluents, pH values, the ratio of phenylboronic acid derivatives (PBAD) to BT (α PBAD/BT ), and A336 to BT (β A336/BT ) on extraction property was investigated in detail. For model BT solutions, satisfactory extraction efficiency of 92% was obtained under the conditions of α PBAD/BT  = 1.5, β A336/BT  = 2, with dichloromethane as a diluent. Aqueous hydrochloric acid solutions were employed to strip BT from the organic phase. For actual fermentation broth, the extraction and stripping efficiency under the optimum conditions were 74% and 69%, respectively. Besides, compared with the original fermentation broth, 1,2,4-butanetriol has been concentrated by 4.6 times with the reactive extraction coupled hydrolysis.

研究领域: 化学工程 · 生物技术 · 有机化学
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