The process based on supercritical fluid extraction for reprocessing of the spent nuclear fuel has some remarkable advantages over the plutonium-uranium extraction(PUREX) process.Especially,it can minimize the generat...The process based on supercritical fluid extraction for reprocessing of the spent nuclear fuel has some remarkable advantages over the plutonium-uranium extraction(PUREX) process.Especially,it can minimize the generation of secondary waste.Dynamic reactive extraction of neodymium oxide(Nd2O3) in supercritical carbon dioxide(SC-CO2) containing tri-n-butyl phosphate-nitric acid(TBP-HNO3) complex was investigated.Temperature showed a positive effect on the extraction efficiency,while pressure showed a negative effect when the unsaturated TBP-HNO3 complex was employed for the dynamic reactive extraction of Nd2O3 in SC-CO2.Both temperature and pressure effects indicated that the kinetic process of the reactive extraction was controlled by the chemical reaction.A kinetic model was proposed to describe the extraction process.展开更多
Extraction of o-aminophenol (OAP) using trialkylphosphine oxide (TRPO) was studied with different diluents. The neutral OAP was extracted using TRPO under an equilibrium pH in the range of 6—7.5, and a maximum distri...Extraction of o-aminophenol (OAP) using trialkylphosphine oxide (TRPO) was studied with different diluents. The neutral OAP was extracted using TRPO under an equilibrium pH in the range of 6—7.5, and a maximum distribution coefficient occurred. It was confirmed that the pH value and the TRPO concentration are the key factors that affect dis-tribution coefficient. Nonpolar diluents could provide better extraction distribution coefficient for the extraction of OAP and the order is: kerosene >n-octanol >chloroform.展开更多
The distributions of nicotinic acid (NA) between water and trialkylamine (N235) dissolved in n-octanol was studied. The complexes of N235 and NA were investigated by Fourier transformation infrared spectrometry to ded...The distributions of nicotinic acid (NA) between water and trialkylamine (N235) dissolved in n-octanol was studied. The complexes of N235 and NA were investigated by Fourier transformation infrared spectrometry to deduce the reaction mechanism. It was found that N235/n-octanol was an efficient extractant for extracting nicotinic acid. The favorable operation conditions were equilibrium aqueous pH 4.2 to 5.5 and initial N235 concentration<0.42 mol·L-1 . The reaction processes included the reaction between neutral N235 and neutral NA and the reaction between protonated N235 and anionic NA. Based on the mass action law and some assumptions, an expression for distribution coefficient D was proposed. The apparent extraction equilibrium constants were calculated by fitting the experimental data and the results were satisfactory.展开更多
2-Ethylhexyl acrylate(2-EHA)is one of the most widely used acrylates in the polymer industry,which is synthesized via Fisher esterification that is limited by chemical equilibrium.To intensify the esterification proce...2-Ethylhexyl acrylate(2-EHA)is one of the most widely used acrylates in the polymer industry,which is synthesized via Fisher esterification that is limited by chemical equilibrium.To intensify the esterification process,in this work,reactive extraction concept is proposed,with halogen-free deep eutectic solvent(DES[Im:2PTSA])as dual solvent-catalyst that consists of imidazole(Im)and p-toluenesulfonamide(PTSA).The bifunctional effects of the DES[Im:2PTSA]are evaluated by thermodynamic analysis and experimental study.Favorable phase splitting is verified byσ-potential analysis predicted by COSMO-RS theory,combined with experiments,and the optimal acid-to-alcohol molar ratio is set to 1.2.The esterification kinetics is then experimentally determined and fitted using the molar-based and activity-based pseudo-homogeneous(PH)models,respectively.The activity-based PH model,that considers the bifunctional roles of the DES,proves to be more accurate with small RMSD of 0.0344.The stability of DES after recycling is validated to further confirm the industrial prospects of DES[Im:2PTSA]in 2-EHA production.展开更多
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 biphasi...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.展开更多
The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl pho...The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl phosphate(TBP), di(2-ethylhexyl) phosphoric acid(D2EHPA) and TBP + D2EHPA dissolved in 1-octanol were investigated, respectively. The influences of the initial concentrations of TBP, D2EHPA and TBP + D2EHPA on distribution ratio(D) were discussed, as well as the reactive extraction mechanism were proposed. The obvious intensification effect was observed when the mixture of TBP and D2EHPA was used as extractant. The best extraction conditions were found to be of the molar ratio of D2EHPA and TBP at 2:1 and the equilibrium aqueous pH at 3.50-4.50. D values increased with the increase of the total concentration of TBP and D2EHPA in 1-octanol. Especially, the analysis on the extraction mechanisms clearly indicate(i) TBP in 1-octanol shows negligible reactive extraction toward 4-HP,(ii) D2EHPA in 1-octanol exhibits moderate extraction effect by forming 4-HP:D2EHPA(1:1) and 4-HP:2D2EHPA(1:2) type complexes, while(iii) D2EHPA in TBP/1-octanol demonstrates the maximum distribution ratio with the 4-HP:D2EHPA(1:1) type complex domination. The discussion provides new insights on the mechanism and opens a new way for the intensified extraction of amphoteric organic compounds by using the mixture of multiple extractants in the diluent.展开更多
Reactive extraction is an emerging technology for large-scale continuous resolution of drug enantiomers. The enantioselective extraction of R,S-naproxen by hydrophilic HP-β-CD in 1,2-dichloroethane was studied at 5℃...Reactive extraction is an emerging technology for large-scale continuous resolution of drug enantiomers. The enantioselective extraction of R,S-naproxen by hydrophilic HP-β-CD in 1,2-dichloroethane was studied at 5℃. The experimental data were described by a reactive extraction model with a homogeneous aqueous phase reaction of R,S-naproxen with HP-β-CD which couples a complete description of chemical equilibria in aqueous phase with the overall phase equilibria of the system. Important parameters of this model were determined experimentally. The physical distribution coefficients for molecular and ionic NAP were 0.041 and 1.730, respectively. Here we show that the efficiency of extraction depends strongly on two process variables including pH and HP-β-CD concentration. The model predictions are compared graphically with the results of pre- vious experiments and there is a good agreement between each other. By the use of modeling and experiment, an optimized extraction condition with pH of 2.5 and HP-β-CD concentration of 0.1 mol/L was obtained with high enantioselectivity （a） of 1.59 and performance factor （pf） of 0,049. The model gives a good means of predicting enantiomers partitioning over a range of experimental conditions.展开更多
The preparation of hydrogen peroxide from anthrahydroquinone by reactive extraction was investigated.The integration process of oxidation of anthrahydroquinone by air and extraction of hydrogen peroxide from the organ...The preparation of hydrogen peroxide from anthrahydroquinone by reactive extraction was investigated.The integration process of oxidation of anthrahydroquinone by air and extraction of hydrogen peroxide from the organic phase with water was carried out in a sieve plate column under pressure.The conversion of anthrahydroquinone increased with increasing pressure resulting in an increase of hydrogen peroxide concentration in the aqueous phase.However,no change in extraction efficiency of hydrogen peroxide was observed.A mathematical model for gas-liquid-liquid reactive extraction was established.In themodel,the effects of pressure and gas superficial velocity on reaction were considered.With increasing gas superficial velocity,the conversion of anthrahydroquinone increased,and the fraction of hydrogen peroxide extracted reached a plateau with a maximum of 72.94%.However,both the conversion of anthrahydroquinone and the fraction of hydrogen peroxide extracted decreased with increasing organic phase superficial velocity.展开更多
The kinetics of the extraction of phenylsuccinic acid(PSA) enantiomers by hydroxypropyl-β-cyclodextrin(HP-β-CD) in a modified Lewis cell was studied,in which HP-β-CD dissolved in 0.1 mol L-1 NaH2PO4/H3PO4 buffer so...The kinetics of the extraction of phenylsuccinic acid(PSA) enantiomers by hydroxypropyl-β-cyclodextrin(HP-β-CD) in a modified Lewis cell was studied,in which HP-β-CD dissolved in 0.1 mol L-1 NaH2PO4/H3PO4 buffer solution(pH = 2.5) was selected as the chiral extractant.PSA enantiomers were extracted from organic phase to aqueous phase in the extraction module.The theory of extraction accompanied by a chemical reaction has been used to obtain the intrinsic kinetics of this extraction module.The different parameters affecting the extraction rate such as agitation speed,interfacial area,initial concentration of PSA enantiomers in organic phase as well as HP-β-CD concentration in aqueous phase were separately studied.The experimental results demonstrate that the extraction reactions are fast.The reactions were found to be first order with respect to PSA and second order with respect to HP-β-CD with forward rate constants of 3.4 × 10-2 m6 mol-2 s-1 for R-PSA and 9.96 × 10?3 m6 mol-2 s-1 for S-PSA.These data will be useful in the design of extraction processes.展开更多
The aqueous solutions are evaluated as sustainable reactive extraction solvents for the recovery of monohydroxyl alcohols （benzyl alcohol, 1-hexanol, cyclohexanol） present in few-percent concentrations in apolar hyd...The aqueous solutions are evaluated as sustainable reactive extraction solvents for the recovery of monohydroxyl alcohols （benzyl alcohol, 1-hexanol, cyclohexanol） present in few-percent concentrations in apolar hydrocarbons （toluene, n-hexane, and cyclohexane） by considering two approaches. An aqueous solution containing a reactive extractant, like borate salts, borate complexes, a monosalt of dicarboxylic acid, hydroxypropyl-cyclodextrins, and silver nitrate, shows limited potential to be used. Another approach, in which the alcohol is chemically modified prior to the extraction into an easy-extractable form, in this case a monoester/carboxylic acid, shows much more potential. An environmentally benign aqueous solution of sodium hydrogen carbonate can provide a distribution ratio of benzyl alcohol up to 200, leaving the solubility of the organic solvent in the aqueous solution unchanged relative to pure water and therefore increasing the selectivity with two orders of magnitude. The modification of aromatic, cyclo-aliphatic, and linear aliphatic alcohols can be performed efficiently in the apolar organic solvent without need for a catalyst. The recovery of the modified alcohol can be performed by back-extraction in combination with a spontaneous hydrolysis.展开更多
Extraction of chromate ions from wastewater by tri alkylamine(R 3N) dissolved in kerosene was studied at 2560℃. 1 Octanol was used as the modifier to remove the third phase. The aqueous phase was a sulfuric acid...Extraction of chromate ions from wastewater by tri alkylamine(R 3N) dissolved in kerosene was studied at 2560℃. 1 Octanol was used as the modifier to remove the third phase. The aqueous phase was a sulfuric acid solution of Cr(Ⅵ) in the concentration range commonly encountered in the galvanizing industry, namely about 2.0 mol/L. Measurement of equilibrium behavior of Cr(Ⅵ) was carried out over wide concentration ranges of amine, Cr 2O 2- 7 and 1 octanol. Experimental results showed that the proper temperatures for extraction are 2540℃ , the [H +] of the aqueous phase is 2 mol/L, and the solvent composition is 30% R 3N, 64% kerosene, and 6% 1 octanol. Prediction and optimization of solvent extraction plant performance for variable industrial feed conditions are then possible. The influence of 1 octanol as the modifier to remove the third phase was also studied.展开更多
p-Amino benzene sulfonic acid (PABSA) is selected as the solute with amphoteric functional group, Lewis acid and Lewis base, to be separated from its dilute solutions. An aliphatic, straight chain amine, Alamine 336 ,...p-Amino benzene sulfonic acid (PABSA) is selected as the solute with amphoteric functional group, Lewis acid and Lewis base, to be separated from its dilute solutions. An aliphatic, straight chain amine, Alamine 336 , is used as the extractant, and kerosene, 1-octanol, chloroform, butyl acetate and benzene as the diluent. The effects of pH value of solution, extractant concentration, salt and types of diluent on the distribution coefficient, D, are studied. There is a peak of D value with pH value of solution, the polar diluents are favorable for extracting PABSA, and the salt in aqueous phase reduces values of D apparently. The extraction equilibrium is described using the mass action law, and the calculated data according to the proposed model agree with the experimental data well. Further, the extraction behavior for other amino benzene sulfonic acids, l-amino-8-naphtol-3,6-disulfonic acid (H acid) and 4,4'-diaminostilbene-2,2'-disulfonic acid (DSD acid), is investigated in a wide pH value region. Finally, H acid and DSD acid are successfully removed from wastewater by the extraction with Alamine 336.展开更多
Enantioselective extraction of hydrophobic clorprenaline （CPE） enantiomers from organic phase to aqueous phases with sulfobutylether-β-cyclodextrin （SBE-β-CD） as the selector was investigated with insight into a...Enantioselective extraction of hydrophobic clorprenaline （CPE） enantiomers from organic phase to aqueous phases with sulfobutylether-β-cyclodextrin （SBE-β-CD） as the selector was investigated with insight into a number of important process variables, such as the type of organic solvent, concentration of selector, pH, and temperature. Equilibrium of the extraction system was modeled using a reactive extraction modcl with a homogeneous aqueous phase reaction. The important parameters of this model were determined experimentally. The physical distribution coefficients for molecular and ionic CPE were determined as 0.3 and 8.93, respectively. The equilibrium constants of the complexation reaction with SBE-β-CD were determined as 152 and 110 L/mol for R- and S-CPE, respectively. Results show that the experimental data agree with the model predictions perfectly. Comprehensively considering the experiment and model, the extraction conditions are optimized and the best extraction conditions are： pH of 6.0, SBE-β-CD concentration of 0.04 tool/L, and temperature of 5 ℃, providing the enantioselectivity （a） of 1.25, the fraction of R-CPE （φR） in aqueous phase of 0.71 and performance factor （pf） of 0.025.展开更多
A new separation method, reactive extractive distillation, was put forward for separating water and acetic acid. The separation mechanism was analyzed through infrared spectra technique. Isobaric vapor-liquid equilibr...A new separation method, reactive extractive distillation, was put forward for separating water and acetic acid. The separation mechanism was analyzed through infrared spectra technique. Isobaric vapor-liquid equilibrium (VLE) data at 101.33 kPa for the binary or ternary systems consisting of water, acetic acid and tributylamine were measured. The activity coefficients were correlated by using Wilson, NRTL, and UNIQUAC Equations.The VLE experiment showed that tributylamine could enhance the relative volatility of water to acetic acid. An extractive distillation experiment was carried out and proved that tributylamine was a good extractive solvent.展开更多
A new reactive and extractive distillation process with ionic liquids as entrainer and catalyst （RED-IL）was proposed to produce methanol and n-butyl acetate by transesterification reaction of methyl acetate with n-b...A new reactive and extractive distillation process with ionic liquids as entrainer and catalyst （RED-IL）was proposed to produce methanol and n-butyl acetate by transesterification reaction of methyl acetate with n-butanol. The RED-IL process was simulated via a rigorous model, and high purity products of methanol and n-butyl acetate can be obtained in such a process. The effects of reflux ratio, feed mode, holdup, feed location, entrainer ratio and catalyst concentration on RED-IL process were investigated. The conversion of methyl acetate and purities of products increase with the holdup in column, entrainer ratio and catalyst content. An optimal reflux ratio exists in RED-IL process. Comparing to the mixed-feed mode, the segregated-feed mode is more effective, in which the optimal feed locations of reactants exist.展开更多
A process for the production of glycerol carbonate(GC) is proposed with the transesterification of glycerol(GL)and dimethyl carbonate(DMC) with CaO as catalyst by reactive distillation and extractive distillation. The...A process for the production of glycerol carbonate(GC) is proposed with the transesterification of glycerol(GL)and dimethyl carbonate(DMC) with CaO as catalyst by reactive distillation and extractive distillation. The performance of solvents in separating DMC-methanol azeotrope and the effects of operation parameters on the reactive distillation process are investigated experimentally. The results indicate that both the GL conversion and GC yield increase with the DMC/GL molar ratio, reflux ratio, final temperature of tower bottom, and CaO/GL molar ratio and decrease as the recycle number of CaO increases. The calcium concentration in the residual reaction mixture also decreases remarkably as the DMC/GL molar ratio increases. At DMC/GL molar ratio 4.0, reflux ratio 1.0, final temperature of tower bottom 358 K, and CaO/GL molar ratio 0.05, both the GL conversion and GC yield can reach above 99.0%, and the mass concentration of calcium in the product is less than 0.08%.展开更多
With Nb-Ti-stabilized 430 ferritic stainless steel（NTS430FSS） and SUS 430 ferritic stainless steel（SUS430FSS） as experimental materials, the influence of precipitation on intergranular corrosion resistance was inv...With Nb-Ti-stabilized 430 ferritic stainless steel（NTS430FSS） and SUS 430 ferritic stainless steel（SUS430FSS） as experimental materials, the influence of precipitation on intergranular corrosion resistance was investigated. A series of aging treatment were carried out. The free-exposure corrosion test and double loop electrochemical potentiokinetic reactivation（DL-EPR） test with a scan rate of 1.67 m V/s at 26 °C were applied to evaluate the intergranular corrosion（IGC） resistance. Metallographic observation, scanning electron microscope（SEM）, transmission electron microscope（TEM） with energy dispersive spectroscopy（EDS） and X-ray diffraction（XRD） analysis were conducted. The results show that IGC occurred in SUS430 FSS aged above 700 °C, while it occurred in NTS430 FSS as the temperature was improved to 1 050 °C. The critical degree of sensitization Ir/Ia reaches 0.305 in SUS430 FSS, which is higher than that of NTS430 FSS, i.e. 0.010, aged at 950 °C for 2 h. The TEM, EDS and XRD results show that a large amount of Cr23C6 precipitates with size of 60 nm×22 nm are located at the SUS430 FSS grain boundaries as chains. With the addition of Nb and Ti and reduction of C, the amount of precipitates reduces significantly in NTS430 FSS. A majority of Cr23C6 were replaced by Ti C and Nb C. Only a small amount of spherical Ti C（R=186 nm） and square Ti N（312 nm×192 nm） with Nb and Cr adsorbed are left along grain boundaries. Due to the dual stabilization of Nb and Ti, the precipitation of Cr23C6 is restrained, the chromium depleted region is avoided and accordingly the resistance to the intergranular corrosion is improved.展开更多
Tertiary amines dissolved in diluents are attractive extractants for recovery of carboxylic acids from dilute aqueous solutions. Quantitative Fourier transform infrared (FTIR) analysis of organic solutions containin...Tertiary amines dissolved in diluents are attractive extractants for recovery of carboxylic acids from dilute aqueous solutions. Quantitative Fourier transform infrared (FTIR) analysis of organic solutions containing various concentrations of trioctylamine (TOA), n octanol, and propionic acid was carried out, and liquid liquid equilibrium was investigated using TOA in n octanol as the solvent. The fraction of ion pair association between TOA and propionic acid in the organic phase was quantitatively determined by FTIR. The apparent reactive extraction equilibrium constant, K 11 , was calculated using the quantitative FTIR spectrum and the equilibrium data. The results show that the fraction of ion pair association depends on diluent concentration, complex dissolution for propionic acid, and association between TOA and propionic acid. The K 11 based on quantitative FTIR has the same loading trend as that from the equilibrium data.展开更多
基金Supported by the National Natural Science Foundation of China （20506014）.
文摘The process based on supercritical fluid extraction for reprocessing of the spent nuclear fuel has some remarkable advantages over the plutonium-uranium extraction(PUREX) process.Especially,it can minimize the generation of secondary waste.Dynamic reactive extraction of neodymium oxide(Nd2O3) in supercritical carbon dioxide(SC-CO2) containing tri-n-butyl phosphate-nitric acid(TBP-HNO3) complex was investigated.Temperature showed a positive effect on the extraction efficiency,while pressure showed a negative effect when the unsaturated TBP-HNO3 complex was employed for the dynamic reactive extraction of Nd2O3 in SC-CO2.Both temperature and pressure effects indicated that the kinetic process of the reactive extraction was controlled by the chemical reaction.A kinetic model was proposed to describe the extraction process.
基金Supported by the Educational Department of Henan Province (No.2004530001).
文摘Extraction of o-aminophenol (OAP) using trialkylphosphine oxide (TRPO) was studied with different diluents. The neutral OAP was extracted using TRPO under an equilibrium pH in the range of 6—7.5, and a maximum distribution coefficient occurred. It was confirmed that the pH value and the TRPO concentration are the key factors that affect dis-tribution coefficient. Nonpolar diluents could provide better extraction distribution coefficient for the extraction of OAP and the order is: kerosene >n-octanol >chloroform.
基金Supported by the Ministry of Education of Henan Province in China (2011A610004)
文摘The distributions of nicotinic acid (NA) between water and trialkylamine (N235) dissolved in n-octanol was studied. The complexes of N235 and NA were investigated by Fourier transformation infrared spectrometry to deduce the reaction mechanism. It was found that N235/n-octanol was an efficient extractant for extracting nicotinic acid. The favorable operation conditions were equilibrium aqueous pH 4.2 to 5.5 and initial N235 concentration<0.42 mol·L-1 . The reaction processes included the reaction between neutral N235 and neutral NA and the reaction between protonated N235 and anionic NA. Based on the mass action law and some assumptions, an expression for distribution coefficient D was proposed. The apparent extraction equilibrium constants were calculated by fitting the experimental data and the results were satisfactory.
基金The financial support from National Natural Science Foundation of China(21776074,21861132019 and 21978096)is greatly acknowledged
文摘2-Ethylhexyl acrylate(2-EHA)is one of the most widely used acrylates in the polymer industry,which is synthesized via Fisher esterification that is limited by chemical equilibrium.To intensify the esterification process,in this work,reactive extraction concept is proposed,with halogen-free deep eutectic solvent(DES[Im:2PTSA])as dual solvent-catalyst that consists of imidazole(Im)and p-toluenesulfonamide(PTSA).The bifunctional effects of the DES[Im:2PTSA]are evaluated by thermodynamic analysis and experimental study.Favorable phase splitting is verified byσ-potential analysis predicted by COSMO-RS theory,combined with experiments,and the optimal acid-to-alcohol molar ratio is set to 1.2.The esterification kinetics is then experimentally determined and fitted using the molar-based and activity-based pseudo-homogeneous(PH)models,respectively.The activity-based PH model,that considers the bifunctional roles of the DES,proves to be more accurate with small RMSD of 0.0344.The stability of DES after recycling is validated to further confirm the industrial prospects of DES[Im:2PTSA]in 2-EHA production.
基金support from National Natural Science Foundation of China(21776074 and 21576081)is greatly acknowledged.
文摘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.
基金supported by the Science and Technology Research Project of Henan Province (192102310490 and 212102310505)。
文摘The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl phosphate(TBP), di(2-ethylhexyl) phosphoric acid(D2EHPA) and TBP + D2EHPA dissolved in 1-octanol were investigated, respectively. The influences of the initial concentrations of TBP, D2EHPA and TBP + D2EHPA on distribution ratio(D) were discussed, as well as the reactive extraction mechanism were proposed. The obvious intensification effect was observed when the mixture of TBP and D2EHPA was used as extractant. The best extraction conditions were found to be of the molar ratio of D2EHPA and TBP at 2:1 and the equilibrium aqueous pH at 3.50-4.50. D values increased with the increase of the total concentration of TBP and D2EHPA in 1-octanol. Especially, the analysis on the extraction mechanisms clearly indicate(i) TBP in 1-octanol shows negligible reactive extraction toward 4-HP,(ii) D2EHPA in 1-octanol exhibits moderate extraction effect by forming 4-HP:D2EHPA(1:1) and 4-HP:2D2EHPA(1:2) type complexes, while(iii) D2EHPA in TBP/1-octanol demonstrates the maximum distribution ratio with the 4-HP:D2EHPA(1:1) type complex domination. The discussion provides new insights on the mechanism and opens a new way for the intensified extraction of amphoteric organic compounds by using the mixture of multiple extractants in the diluent.
基金supported by the National Natural Science Foundation of China (20976041)Program for New Century Excellent Talents in University,Hunan Provincial Natural Science Foundation (10JJ1004)+1 种基金Aid Program for Science and Technology Innovative Research Team in Higher Educational Instituions of Hunan Provincethe Open Fund Project of Key Laboratory in Hunan University (09K095)
文摘Reactive extraction is an emerging technology for large-scale continuous resolution of drug enantiomers. The enantioselective extraction of R,S-naproxen by hydrophilic HP-β-CD in 1,2-dichloroethane was studied at 5℃. The experimental data were described by a reactive extraction model with a homogeneous aqueous phase reaction of R,S-naproxen with HP-β-CD which couples a complete description of chemical equilibria in aqueous phase with the overall phase equilibria of the system. Important parameters of this model were determined experimentally. The physical distribution coefficients for molecular and ionic NAP were 0.041 and 1.730, respectively. Here we show that the efficiency of extraction depends strongly on two process variables including pH and HP-β-CD concentration. The model predictions are compared graphically with the results of pre- vious experiments and there is a good agreement between each other. By the use of modeling and experiment, an optimized extraction condition with pH of 2.5 and HP-β-CD concentration of 0.1 mol/L was obtained with high enantioselectivity （a） of 1.59 and performance factor （pf） of 0,049. The model gives a good means of predicting enantiomers partitioning over a range of experimental conditions.
文摘The preparation of hydrogen peroxide from anthrahydroquinone by reactive extraction was investigated.The integration process of oxidation of anthrahydroquinone by air and extraction of hydrogen peroxide from the organic phase with water was carried out in a sieve plate column under pressure.The conversion of anthrahydroquinone increased with increasing pressure resulting in an increase of hydrogen peroxide concentration in the aqueous phase.However,no change in extraction efficiency of hydrogen peroxide was observed.A mathematical model for gas-liquid-liquid reactive extraction was established.In themodel,the effects of pressure and gas superficial velocity on reaction were considered.With increasing gas superficial velocity,the conversion of anthrahydroquinone increased,and the fraction of hydrogen peroxide extracted reached a plateau with a maximum of 72.94%.However,both the conversion of anthrahydroquinone and the fraction of hydrogen peroxide extracted decreased with increasing organic phase superficial velocity.
基金supported by the National Natural Science Foundation of China (20976041)Program for New Century Excellent Talents in University,Hunan Provincial Natural Science Foundation of China (10JJ1004)the Open Fund Project of Key Laboratory in Hunan University (09K095)
文摘The kinetics of the extraction of phenylsuccinic acid(PSA) enantiomers by hydroxypropyl-β-cyclodextrin(HP-β-CD) in a modified Lewis cell was studied,in which HP-β-CD dissolved in 0.1 mol L-1 NaH2PO4/H3PO4 buffer solution(pH = 2.5) was selected as the chiral extractant.PSA enantiomers were extracted from organic phase to aqueous phase in the extraction module.The theory of extraction accompanied by a chemical reaction has been used to obtain the intrinsic kinetics of this extraction module.The different parameters affecting the extraction rate such as agitation speed,interfacial area,initial concentration of PSA enantiomers in organic phase as well as HP-β-CD concentration in aqueous phase were separately studied.The experimental results demonstrate that the extraction reactions are fast.The reactions were found to be first order with respect to PSA and second order with respect to HP-β-CD with forward rate constants of 3.4 × 10-2 m6 mol-2 s-1 for R-PSA and 9.96 × 10?3 m6 mol-2 s-1 for S-PSA.These data will be useful in the design of extraction processes.
基金Supported by DSM, NWO-CW (Netherlands Organisation for Scien-tific Research-Chemical Science) and NOVEM (Netherlands Agency for Energy and Environment)
文摘The aqueous solutions are evaluated as sustainable reactive extraction solvents for the recovery of monohydroxyl alcohols （benzyl alcohol, 1-hexanol, cyclohexanol） present in few-percent concentrations in apolar hydrocarbons （toluene, n-hexane, and cyclohexane） by considering two approaches. An aqueous solution containing a reactive extractant, like borate salts, borate complexes, a monosalt of dicarboxylic acid, hydroxypropyl-cyclodextrins, and silver nitrate, shows limited potential to be used. Another approach, in which the alcohol is chemically modified prior to the extraction into an easy-extractable form, in this case a monoester/carboxylic acid, shows much more potential. An environmentally benign aqueous solution of sodium hydrogen carbonate can provide a distribution ratio of benzyl alcohol up to 200, leaving the solubility of the organic solvent in the aqueous solution unchanged relative to pure water and therefore increasing the selectivity with two orders of magnitude. The modification of aromatic, cyclo-aliphatic, and linear aliphatic alcohols can be performed efficiently in the apolar organic solvent without need for a catalyst. The recovery of the modified alcohol can be performed by back-extraction in combination with a spontaneous hydrolysis.
基金the National Natural Science Foundationof China(No.2 9836 130
文摘Extraction of chromate ions from wastewater by tri alkylamine(R 3N) dissolved in kerosene was studied at 2560℃. 1 Octanol was used as the modifier to remove the third phase. The aqueous phase was a sulfuric acid solution of Cr(Ⅵ) in the concentration range commonly encountered in the galvanizing industry, namely about 2.0 mol/L. Measurement of equilibrium behavior of Cr(Ⅵ) was carried out over wide concentration ranges of amine, Cr 2O 2- 7 and 1 octanol. Experimental results showed that the proper temperatures for extraction are 2540℃ , the [H +] of the aqueous phase is 2 mol/L, and the solvent composition is 30% R 3N, 64% kerosene, and 6% 1 octanol. Prediction and optimization of solvent extraction plant performance for variable industrial feed conditions are then possible. The influence of 1 octanol as the modifier to remove the third phase was also studied.
基金Supported by the National Natural Science Foundation of China (No. 29836130).
文摘p-Amino benzene sulfonic acid (PABSA) is selected as the solute with amphoteric functional group, Lewis acid and Lewis base, to be separated from its dilute solutions. An aliphatic, straight chain amine, Alamine 336 , is used as the extractant, and kerosene, 1-octanol, chloroform, butyl acetate and benzene as the diluent. The effects of pH value of solution, extractant concentration, salt and types of diluent on the distribution coefficient, D, are studied. There is a peak of D value with pH value of solution, the polar diluents are favorable for extracting PABSA, and the salt in aqueous phase reduces values of D apparently. The extraction equilibrium is described using the mass action law, and the calculated data according to the proposed model agree with the experimental data well. Further, the extraction behavior for other amino benzene sulfonic acids, l-amino-8-naphtol-3,6-disulfonic acid (H acid) and 4,4'-diaminostilbene-2,2'-disulfonic acid (DSD acid), is investigated in a wide pH value region. Finally, H acid and DSD acid are successfully removed from wastewater by the extraction with Alamine 336.
基金Projects(21176262,21071052) supported by the National Natural Science Foundation of ChinaProject supported by the Aid program for Technology Innovative Research Team in Higher Educational Institutions of Hunan Province,China
文摘Enantioselective extraction of hydrophobic clorprenaline （CPE） enantiomers from organic phase to aqueous phases with sulfobutylether-β-cyclodextrin （SBE-β-CD） as the selector was investigated with insight into a number of important process variables, such as the type of organic solvent, concentration of selector, pH, and temperature. Equilibrium of the extraction system was modeled using a reactive extraction modcl with a homogeneous aqueous phase reaction. The important parameters of this model were determined experimentally. The physical distribution coefficients for molecular and ionic CPE were determined as 0.3 and 8.93, respectively. The equilibrium constants of the complexation reaction with SBE-β-CD were determined as 152 and 110 L/mol for R- and S-CPE, respectively. Results show that the experimental data agree with the model predictions perfectly. Comprehensively considering the experiment and model, the extraction conditions are optimized and the best extraction conditions are： pH of 6.0, SBE-β-CD concentration of 0.04 tool/L, and temperature of 5 ℃, providing the enantioselectivity （a） of 1.25, the fraction of R-CPE （φR） in aqueous phase of 0.71 and performance factor （pf） of 0.025.
文摘A new separation method, reactive extractive distillation, was put forward for separating water and acetic acid. The separation mechanism was analyzed through infrared spectra technique. Isobaric vapor-liquid equilibrium (VLE) data at 101.33 kPa for the binary or ternary systems consisting of water, acetic acid and tributylamine were measured. The activity coefficients were correlated by using Wilson, NRTL, and UNIQUAC Equations.The VLE experiment showed that tributylamine could enhance the relative volatility of water to acetic acid. An extractive distillation experiment was carried out and proved that tributylamine was a good extractive solvent.
基金Supported by the Innovation Fund of Tianjin University
文摘A new reactive and extractive distillation process with ionic liquids as entrainer and catalyst （RED-IL）was proposed to produce methanol and n-butyl acetate by transesterification reaction of methyl acetate with n-butanol. The RED-IL process was simulated via a rigorous model, and high purity products of methanol and n-butyl acetate can be obtained in such a process. The effects of reflux ratio, feed mode, holdup, feed location, entrainer ratio and catalyst concentration on RED-IL process were investigated. The conversion of methyl acetate and purities of products increase with the holdup in column, entrainer ratio and catalyst content. An optimal reflux ratio exists in RED-IL process. Comparing to the mixed-feed mode, the segregated-feed mode is more effective, in which the optimal feed locations of reactants exist.
基金Supported by the National Natural Science Foundation of China(21106050)Specialized Research Fund for the Doctoral Program of Higher Education(20100142120066)
文摘A process for the production of glycerol carbonate(GC) is proposed with the transesterification of glycerol(GL)and dimethyl carbonate(DMC) with CaO as catalyst by reactive distillation and extractive distillation. The performance of solvents in separating DMC-methanol azeotrope and the effects of operation parameters on the reactive distillation process are investigated experimentally. The results indicate that both the GL conversion and GC yield increase with the DMC/GL molar ratio, reflux ratio, final temperature of tower bottom, and CaO/GL molar ratio and decrease as the recycle number of CaO increases. The calcium concentration in the residual reaction mixture also decreases remarkably as the DMC/GL molar ratio increases. At DMC/GL molar ratio 4.0, reflux ratio 1.0, final temperature of tower bottom 358 K, and CaO/GL molar ratio 0.05, both the GL conversion and GC yield can reach above 99.0%, and the mass concentration of calcium in the product is less than 0.08%.
文摘With Nb-Ti-stabilized 430 ferritic stainless steel（NTS430FSS） and SUS 430 ferritic stainless steel（SUS430FSS） as experimental materials, the influence of precipitation on intergranular corrosion resistance was investigated. A series of aging treatment were carried out. The free-exposure corrosion test and double loop electrochemical potentiokinetic reactivation（DL-EPR） test with a scan rate of 1.67 m V/s at 26 °C were applied to evaluate the intergranular corrosion（IGC） resistance. Metallographic observation, scanning electron microscope（SEM）, transmission electron microscope（TEM） with energy dispersive spectroscopy（EDS） and X-ray diffraction（XRD） analysis were conducted. The results show that IGC occurred in SUS430 FSS aged above 700 °C, while it occurred in NTS430 FSS as the temperature was improved to 1 050 °C. The critical degree of sensitization Ir/Ia reaches 0.305 in SUS430 FSS, which is higher than that of NTS430 FSS, i.e. 0.010, aged at 950 °C for 2 h. The TEM, EDS and XRD results show that a large amount of Cr23C6 precipitates with size of 60 nm×22 nm are located at the SUS430 FSS grain boundaries as chains. With the addition of Nb and Ti and reduction of C, the amount of precipitates reduces significantly in NTS430 FSS. A majority of Cr23C6 were replaced by Ti C and Nb C. Only a small amount of spherical Ti C（R=186 nm） and square Ti N（312 nm×192 nm） with Nb and Cr adsorbed are left along grain boundaries. Due to the dual stabilization of Nb and Ti, the precipitation of Cr23C6 is restrained, the chromium depleted region is avoided and accordingly the resistance to the intergranular corrosion is improved.
基金the National Natural Science Foundationof China(No. 2 9836 130 )
文摘Tertiary amines dissolved in diluents are attractive extractants for recovery of carboxylic acids from dilute aqueous solutions. Quantitative Fourier transform infrared (FTIR) analysis of organic solutions containing various concentrations of trioctylamine (TOA), n octanol, and propionic acid was carried out, and liquid liquid equilibrium was investigated using TOA in n octanol as the solvent. The fraction of ion pair association between TOA and propionic acid in the organic phase was quantitatively determined by FTIR. The apparent reactive extraction equilibrium constant, K 11 , was calculated using the quantitative FTIR spectrum and the equilibrium data. The results show that the fraction of ion pair association depends on diluent concentration, complex dissolution for propionic acid, and association between TOA and propionic acid. The K 11 based on quantitative FTIR has the same loading trend as that from the equilibrium data.
