Removal of mercaptans from light oils using ionic liquid–NaOH aqueous solution as extractants

The application of ionic liquids as alternatives to conventional organic solvents in the extraction process has been investigated. In the present study, fourteen species of imidazolium-based ionic liquids were added into the Na OH(aq) to remove the mercaptans. The influences of anion species and cation alkyl chain length of the imidazolium-based ionic liquids on the performance of mercaptan removal from light oils have been discussed.The efficiency of extraction for mercaptans exhibited the order of [Ac]~-N [OH]~-≈ [Br]~-N [BF4]~-. The longer alkyl chain imidazolium-based ionic liquids contributed to enhance desulfurization rate of 1-butyl mercaptan.100% desulfurization rate of 1-butyl mercaptan was achieved by the anion of Ac-ionic liquids and Na OH(aq)at a volume ratio of 40:1(V(oil):V(ionic liquid)) and a short equilibrium time within 10 min.     

Direct extraction of Mo(Ⅵ) from sulfate solution by synergistic extractants in the rotation column

Direct extraction of molybdenum from sulfate solution with synergistic extractants(mixture of D_2EHPA and TBP)was studied in the rotation column. The influence of extractant concentration and initial pH of aqueous phase was studied in the bench scale experiments. The outcomes demonstrated that the synergistic solvent extraction enhances the constancy of the extracted complexes for transfer into the organic phase. In the continuous experiments, the effect of different operating parameters such as speed of agitation, inlet solvent flow rate and inlet aqueous flow rate on the holdup, mean drop size, drop size distribution, slip and characteristic velocities and extraction percentage were examined. Modified correlations were proposed for prediction of hydrodynamic parameters with consideration of reaction extraction condition in the rotation column. Furthermore, these correlations were compared with the experimental data. According to the results, the direct extraction of Mo(Ⅵ) from aqueous solution and sulfuric media with extraction efficiency of 90.4% was obtained at higher rotor speed(240 r·min~(–1) rpm) in this column.     

新型己内酰胺萃取剂的筛选和评价

Mixed solvent of 1-octanol and cyclohexane with 60% （by mass） 1-octanol content was selected as a new extractant for caprolactam extraction. Compared with benzene or toluene, the new extractant has larger extraction capacity and much lower toxicity. Although the extraction capacity of the new extractant is smaller than that of pure 1-octanol, 1-octanol solubility of the new extractant in aqueous phase is much smaller. Because of its physical properties of lower density, lower viscosity, and higher interfacial tension, the new extractant performed much better phase separation ability than pure 1-octanol. The new extractant showed certain selectivity when dealing with lactam oil. The mixed solvent of 1-octanol and cyclohexane with 60% （by mass） 1-octanol content is a promising extractant for caprolactam extraction.     

Solvent extraction of lanthanum and cerium ions from hydrochloric acidic aqueous solutions using partly saponified 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester

In order to clarify the extraction process with saponified extractant, the solvent extraction experiments of rare earth elements(REEs), lanthanum and cerium, by using partly saponified 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester(EHEHPA, HL) from hydrochloric acidic solutions have been performed. The concentration of initial aqueous rare earth ion was in a range of 0.0010–0.1000 mol·L~(-1); EHEHPA in a range of 0.2877–0.8631 mol·L~(-1) with saponification rate of 0.3(mole fraction), and the initial aqueous p H in a range of 1.00–4.00. Firstly, the extracted species were determined by the saturation extraction capacity method. Secondly, according to the equilibrium aqueous pH values, the extraction processes were divided into three different categories: extraction with saponified EHEHPA, extraction with un-saponified EHEHPA, and hydrolysis process. Finally, for the first two processes, in order to predict the distribution ratio, two semi-empirical calculation models were developed with.The calculation results are in good agreement well with the experimental data.     

Kinetics and the difference for extraction of praseodymium and neodymium from nitrate aqueous solution by[A336] [NO3] using the single drop technique

The kinetics and the difference for Pr(Ⅲ) and Nd(Ⅲ) extraction from nitrate aqueous solution using trialkylmethylammonium nitrate([A336][NO_3]) as extractant were investigated by the single drop technique.The dependence of the extraction rate of Pr(Ⅲ) and Nd(Ⅲ) on the concentrations of free Pr(Ⅲ) and Nd(Ⅲ)ions, the concentrations of Na NO_3 and H~+in aqueous solutions, and the concentrations of [A336][NO_3] in kerosene solutions were discussed and the corresponding extraction rate equations for Pr(Ⅲ) and Nd(Ⅲ) were obtained. These equations demonstrated that the reaction rate constant of Pr(Ⅲ) with [A336][NO_3] was double than that of Nd(Ⅲ). The effect of the addition of diethylenetriaminepentaacetic acid(DTPA) on the difference in the extraction rate of Pr(Ⅲ) and Nd(Ⅲ) by [A336][NO_3] was also investigated. It was revealed that the difference in the complex formation rates of Pr(Ⅲ) and Nd(Ⅲ) with DTPA made a significant impact on the difference in the extraction rates of Pr(Ⅲ) and Nd(Ⅲ) with [A336][NO_3]. The ratio of extraction rates of Pr(Ⅲ) to Nd(Ⅲ) with[A336][NO_3] was in proportion to the ratio of complex formation rates of Pr(Ⅲ) to Nd(Ⅲ) with DTPA. The extraction rate difference for Pr(Ⅲ) and Nd(Ⅲ) with [A336][NO_3] increased due to a higher complex formation rate constant of DTPA with the free and un-complexed Nd(Ⅲ) ions in the aqueous nitrate solution than that with Pr(Ⅲ) ions. Therefore, the addition of DTPA in the aqueous nitrate solution is an effective method to intensify the separation of Pr(Ⅲ) and Nd(Ⅲ) in kinetics. The study on the extraction mechanism indicated that both the extraction of Pr(Ⅲ) and Nd(Ⅲ) by [A336][NO_3] were diffusion controlled, and the reactions obeyed SN2 mechanism. The present work highlights a possible approach to strengthen the kinetic separation of Pr(Ⅲ) and Nd(Ⅲ).     

Kinetics of Forward Extraction of Boric Acid from Salt Lake Brine by 2-Ethyl-1,3-hexanediol in Toluene Using Single Drop Technique

The kinetics of forward extraction of boric acid from salt lake brine by 2-ethyl-1,3-hexanediol in tolu-ene was investigated using the single drop technique. The factors affecting the extraction rate include interfacial area between aqueous phase and organic phase, initial concentration of boric acid in aqueous phase, initial concen-tration of 2-ethyl-1,3-hexanediol in organic phase, and extraction temperature. The experimental results show that the extraction rate increases with the increase of the initial concentration of boric acid and 2-ethyl-1,3-hexanediol, interfacial area of two phases, and temperature. With the temperature-dependence study, it is showed that the ex-traction is a diffusion-controlled process. The kinetic equation is presented for pH 1.0 in the aqueous phase and temperature of 318 K.     

离心萃取器提取对甲酚的实验和模拟研究

In this study, extraction of p-cresol from the simulated wastewater has been studied using centrifugal extractors and QH-1 extractant. The distribution ratio of p-cresol was approximately 308.5 in the QH-1-p-cresol （pH =2.0） system. The extraction stage efficiency of the single-stage centrifugal extractor was higher than 92%, and the extraction rate of the three-stage cascade was higher than 99%. When 15% NaOH was used for the stripping of p-cresol in QH-1 solution, the stripping rate of the three-stage cascade reached 100%. A mathematical model of multistage countercurrent extraction process that considers the phase volume change, extraction stage efficiency, and phase entrainment was used to simulate the extraction of p-cresol using centrifugal extractors. The calculated results using this model were in good agreement with the experimental results.     

预分散溶剂萃取分离苯酚溶液的研究

Predispersed solvent extraction (PDSE) is a new method for separating solutes from aqueous solution by solvent extraction and one which has shown promise for extraction from extremely dilute solution very efficient and very quick. The use of colloidal liquid aphrons in predispersed solvent extraction may ameliorate the problems such as emulsion formation, reduction of interracial mass transfer and low interfacial mass transfer areas in solvent extraction process. In present paper, colloidal liquid aphrons are successfully generated using kerosene as a solvent,tributyl phosphate(TBP) as an extractant, sodium dodecyl benzene sulphate(SDBS) as surfactant in aqueous phase and Tween-80 in oil phase. Extraction of phenol from dilute solution was studied by using colloidal liquid aphrons and colloidal gas aphrons in a semi-batch extraction column. It has been found that the PDSE process is more suitable for extraction of dilute solutions. It has also been discovered that the PDSE process has a great advantage over traditional single-stage extraction process.     

Recovery of Copper from Leaching Solution of Copper Smelting Ash

An efficient and reliable approach based on solvent extraction to selectively recover copper from leaching solution of Jinchuan copper smelting ash has been developed in this work. And the extraction isotherm of 50%(j) N902 with initial aqueous acidity of 19.6 g/L was determined at 25℃. The results show that the extractant, N902, has good selectivity to copper, and its saturated capacity of copper under the given conditions is over 23 g/L. The recovery rate of copper in the extraction is over 99%. And copper extraction equilibrium is reached in 90 s using 50% N902 with kerosene as the diluenting agent at an organic and aqueous volume phase ratio (O/A) of 1. Furthermore, over 99.5% of the loaded copper in the organic phase could be stripped by applying 196 g/L H2SO4 as the stripping agent.     

Extraction of Lithium from Brine Containing High Concentration of Magnesium by Tri-n-Butyl Phosphate Dissolved in Kerosene

Tri-n-butyl phosphate(TBP)dissolved in kerosene was chosen as extractant for lithium from a modelbrine having high magnesium-to-lithium ratio and ferric chloride was added to the system.The influences of con-tact time,concentration of the extractant,concentrations of some salts(Mg~(2 ), Na~ ,K~ )in the solution,acid-ity of hydrochloric acid and extraction temperature on the exttaction of lithium with TBP-kerosene system werestudied.The suitable extraction conditions were found to be:contact time not any less than 20min;at 20-25C;[Fe~( 3)]/[Li~( )]about 1.5-2.0;TBP concentration 50%-70%;[MgCl_2]exceeding 3 mol·L~(-1);pH about 2;while most sodium and potassium salts in the aqueous phase should be removed before the extraction.     

具有羧酸官能团的功能性离子液体萃取分离钇的研究(英文)

A new kind of hydrophobic ionic liquids [1-alkyl-3-(1-carboxylpropyl)im][PF6] has been synthesized,and their extraction properties for Y(III) in the nitric acid medium was also investigated.The effects of extractant concentration,equilibrium pH of aqueous phase,salt concentration,temperature etc.were discussed.The results show that this kind of Task-Specific Ionic Liquid(TSIL) needs to be saponified before being used for the Y(III) ex-traction,and the extraction is acid dependent,and the extraction efficiency increases with the aqueous phase acidity decreasing.Furthermore,the loaded organic phase is easy to be stripped;more than 95% Y(III) could be stripped from the loaded organic phase when the stripping acidity is higher than 0.07 mol?L?1.The slope analysis technique is used to investigate the extraction mechanism,and a possible cation-exchange extraction mechanism is proposed in the present extraction system.     

三烷基胺萃取氨基磺酸及其废水的特性研究

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, 1-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.     

Enhanced Recovery of Resveratrol and Emodin from Polygonum cuspidatum by a Simultaneous Extraction and Acid Hydrolysis Process

A novel and efficient extraction/hydrolysis method was developed for the recovery of resveratrol and emodin from a well-known traditional chinese medicinal herb, Polygonum cuspidatum. By using a 85% aqueous acetone solution containing 1.0 mol/L HCl as extractant, extraction of resveratrol and emodin from P. cuspidatum and conversion of resveratrol-3-O-β-glucoside and emodin-8-O-β-D-glucoside into the products could be achieved in one step. The effects of several key parameters including concentration of HCl and acetone, temperature, ratio of solvent to material, extraction duration and extraction times on the process efficiency was systematically investigated. The results showed that the optimal conditions for maximizing the recovery yield were 85% acetone containing 1.0 mol/L HCl as extractant, temperature 70 ℃, ratio of liquid to solid 50 mL /g and extraction duration 30 min. This one-pot extraction/hydrolysis process increased the yield of resveratrol and emodin to 524% and 302%, respectively, compared to a raw sample without hydrolysis. Compared with conventional method, the developed process not only achieved high yield of resveratrol and emodin, but simplified the procedures and reduced time. The results demonstrated that the simultaneous extraction/hydrolysis process is simple and efficient which could act as a useful approach for enhanced recovery of resveratrol and emodin from P. cuspidatum.     

Synergistic Extraction of Gallium from Sulfate Solution

A novel extractant mixture, di-2-ethylhexyl phosphate (DEHPA) plus HX, was proposed and tested for recovering gallium from sulfate solution. It was found that the extraction capacity of DEPHA for gallium from sulfate solution could be enhanced significantly due to the synergistic effect of acidic extractant HX. Gallium extraction is negligible below pH 0 and highly sensitive to pH of aqueous phase in the range from 0 to 1, and satisfactory extraction can be gained at pH>1. More than 96% Ga extraction was obtained using 15% DEHPA plus 2% HX. Although Fe (Ⅲ) was found to be extracted preferentially to Ga (Ⅲ), effective extraction of Ga (Ⅲ) was possible by reducing ferric to the ferrous state prior to extraction. A loaded organic phase containing 0.48g L-1 Ga could be produced from solution of 0.12g L-1 Ga at A/O ratio of 4 : 1 via three mixer-settler operation stages. Gallium was stripped quantitatively from the loaded organic phase with l,5mol L-1 of sulfuric acid.     

表面活性剂双水相分离茶多酚生产废液中的茶氨酸(英文)

Extraction of theanine from waste liquid of tea polyphenol production was studied in aqueous surfactant two-phase system (ASTP) with cationic surfactant (CTAB) and anionic surfactant (SDS). Results indicate that the region of ASTP is narrow and there is only a two-phase region of cationic surfactant. The increase in concentrations of NaBr and Na2SO4 are beneficial to the formation of ASTP. Theanine concentration in the bottom phase increases with increasing concentration of theanine, whereas the partition coefficient and extraction rate only change a little when the concentration of theanine is above 0.2 g·L-1 . With the increase of SDS concentration, the phase ratio and the partition coefficient decrease, while the extraction efficiency of theanine increases and the concentration of theanine changes a little in the range from 2.4/7.5 to 2.8/7.2 for SDS/CTAB ratio. The temperature has a notable effect on the concentration of theanine in the bottom phase, partition coefficient and extraction rate of theanine. The increase of waste liquid decreases the phase ratio, increases the concentration and extraction rate of theanine in the bottom phase, since the protein and the saccharide enter the bottom phase with theanine.     

从硫酸盐溶液中协同萃取镓

A novel extractant mixture, di-2-ethylhexyl phosphate (DEHPA) plus HX, was proposed and tested for recovering gallium from sulfate solution. It was found that the extraction capacity of DEPHA for gallium from sulfate solution could be enhanced significantly due to the synergistic effect of acidic extractant HX. Gallium extraction is negligible below pH 0 and highly sensitive to pH of aqueous phase in the range from 0 to 1, and satisfactory extraction can be gained at pH＞1. More than 96% Ga extraction was obtained using 15% DEHPA plus 2% HX. Although Fe (Ⅲ) was found to be extracted preferentially to Ga (Ⅲ), effective extraction of Ga (Ⅲ) was possible by reducing ferric to the ferrous state prior to extraction. A loaded organic phase containing 0.48g. L-1 Ga could be produced from solution of 0.12g@L-1 Ga at A/O ratio of 4: 1 via three mixer-settler operation stages.Gallium was stripped quantitatively from the loaded organic phase with 1.5 mol@L-1 of sulfuric acid.     

Kinetic study on selective extraction of HCl and H3PO4 in a microfluidic device☆

In the extraction method for preparing KH2PO4, one of the key processes is the selective extraction of HCl over H3PO4. In our work, extraction kinetic studies have been carried out in a microfluidic device with a coaxial microchannel, using the extractant of 33.3%(by volume) trioctylamine (TOA) dissolved in n-octanol, with differ-ent aqueous phases:the HCl solution, the H3PO4 solution, and H3PO4 and KCl solutions of different concentra-tions. The changes of the extraction efficiency of HCl and H3PO4 and the selectivity for HCl along with the residence time were investigated. We found that fast extraction kinetics could be realized in microfluidic devices, and that HCl could be extracted faster than H3PO4 due to smaller mass transfer resistance and much stronger re-action between HCl and TOA. For the extraction of H3PO4 and KCl solutions, the selectivity for HCl first increased and then decreased when TOA was in excess of H3PO4 in the initial feeds, and in contrast, always increased when H3PO4 was in excess of TOA in the initial feeds. The diverse changes of selectivity for HCl along with the residence time indicate that a dynamic control of selectivity in microfluidic devices may be important and accessible for im-proving the KH2PO4 conversion efficiency in extraction method.     

Kinetic study on reactive extraction of phenylalanine enantiomers with BINAP-copper complexes

Enantioselective liquid–liquid extraction has attracted considerable attention for its potential use in large-scale production. Kinetic data are needed for the reliable scale-up of the process. This paper reports the kinetic study of reactive extraction of phenylalanine (Phe) enantiomers with BINAP–copper complex (BINAP–Cu) as a chiral selector. The theory of extraction accompanied by a chemical reaction was applied. The effects of agitation speed, interfacial area, pH value of aqueous phase, initial concentration of Phe enan-tiomers and initial concentration of BINAP–Cu on the specific rate of extraction were investigated. The for-ward rate constants of the reactions in the reactive extraction process are 7.93 × 10?5 m5/2·mol?1/2·s?1 for D-Phe and 1.29 × 10?4 m5/2·mol?1/2·s?1 for L-Phe.     

Grouping separation of mixed rare earths from their coexisting aqueous solutions by liquid-column elution

A new approach was proposed for grouping separation of 14 lanthanide rare-earth ions from their coexisting mixed aqueous solutions, by performing liquid-column elution using the aqueous solution containing 14 lanthanide rare-earth ions as the stationary phase and the dispersed organic oil droplets containing P507 extractant as the mobile phase. It was revealed that 14 lanthanide rare-earth ions could be separated into four groups, according to the lanthanide tetrad effect, respectively eluting out from the liquid column at different time in a certain order. Various effects including the saponification degree of P507, the concentration of P507 in organic phase, the length and inner diameter of the extraction column on the performance of grouping separation of rare-earth ions were discussed. The changes of the mass transfer coefficients were also investigated. The separation efficiency of the four groups of rareearth elements(REEs) was evaluated based on the elution resolution, Rs, of the elution peaks of La(Ⅲ),Gd(Ⅲ), Ho(Ⅲ) and Lu(Ⅲ), the four representative elements respectively from each of the four groups of REEs. Experimental results demonstrated that the separation of REEs by liquid-column elution mainly depended on the competitive adsorption of different rare-earth groups onto the surface of ascending P507 oil droplets. The affinity of different rare-earth groups with P507 extractant and a limited adsorption capacity of P507 molecules at the surface of the oil droplets ascending in liquid column play the important role. The present work highlights a promising technique for grouping separation of multiple lanthanide elements co-existing complex systems.