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.     

Extraction Equilibria of Trimellitic and [ 1,1′-Biphenyl]-2,2′-dicarboxylic Acid with 1-Octanol, 50%TBP,and 10%TRPO in Kerosene

To explore the feasibility of extracting aromatic acid products from oxidizing coal, two aromatic acids, trimellitic and [1,1′-biphenyl]-2,2′-dicarboxylic acid, were selected as the solutes, and the extraction equilibrium of the acids were studied with 1-octanol, 50% tributyl phosphate （TBP） in kerosene, and 10% trialkylphosphine oxide （TRPO） in kerosene. The results showed that the degree of extraction of [1,1′-biphenyl]-2,2′-dicarboxylic acid was larger than that of trimellitic acid for all of the solvent, and the extraction capacity with TRPO is more effective than the one with TBP. The extraction behavior of aromatic polyacid is different from that of carboxylic acid, and the reactive extraction function of aromatic acids with TBP and TRPO is not as effective as that of carboxylic acid. 1-octanol could be used to remove [1,1′-biphenyl]-2,2′-dicarboxylic acid from the mixture of trimellitic acid and [1,1′-biphenyl]-2,2′-dicarboxylic acid. Because the weak hydrogen bond association exists between -OH in 1-octanol and -COOH in aromatic acid, the extractive selectivity of [ 1, 1′-biphenyl]-2,2′-dicarboxylic to trimellitic acid depends on the stoichiometric ratio.     

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.     

Emulsion liquid membrane for selective extraction of Bi(III)

Di(2-ethylhexyl)phosphoric acid was used as extractant of bismuth ions from nitrate medium by emulsion liquid membrane, with Triton X-100 as the biodegradable surfactant in n-pentanol bulk membrane. The novelties and innovative points of this work are the application of emulsion liquid membrane for selective and efficient extraction of bismuth ions as wel as the relevant optimization procedures. The extraction of bismuth ions was evaluated by the yield of extraction. The experimental parameters were evaluated and optimized, including the ratio of di(2-ethylhexyl)phosphoric acid mass concentration to Triton X-100 (1.0%:0.5%), nature of diluent (n-pentanol), nature and concentration of stripping solution (sulfuric acid, 0.5 mol·L?1), stirring speed (1800 r·min?1) and equilibrium time of extraction (20 min), initial feed solution of bismuth (350 mg·L?1) and the volume ratio of internal stripping phase to membrane phase (14). The experimental parameters of kinetic extraction reveal that the bismuth ions can be extracted by 100%.     

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.     

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).     

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.     

TBP, MIBK/FeCl3与Li形成萃合物组成的研究（英文）

To study the characteristic of liquid-liquid extraction equilibrium of lithium from brine sources,the complexes formed from tributyl phosphate(TBP) and methyl isobutyl ketone(MIBK) with lithium were investi-gated using FeCl3 as coextracting agent.Liquid-liquid extraction reaction mechanisms were proposed and the stoichiometry of tetrachloroferrate(III) complex with lithium was obtained by regressing the experimental data.It is found that the stoichiometry of tetrachloroferrate(III) to lithium in the complex is 1︰1 with either TBP or MIBK as extractant in kerosene.The stoichiometry of the complex of TBP with Li was 1︰1 and that of MIBK with Li was 2︰1.The formed complexes of TBP and MIBK with lithium are determined to be LiFeCl4?TBP and LiFeCl4?2MIBK,respectively,according to the rule of neutralization.     

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.     

有机溶剂原位萃取法提高悬浮培养中国红豆杉细胞紫杉醇产量

The production of paclitaxel from suspension culture of Taxus chinensis var,mairei was improved by in situ extraction with organic solvents to avoid feedback repression and product degradation.Oleic acid and dibutyl phthalate were proved to be suitable solvents .The optimal volumetric percentage of organic solvents in the culture medium was found to be around 8%,and the favorable time for their introduction was at the exponential phase of cell growth,Paclitaxel production with the in situ extraction was ca 3-fold of that without extraction.     

Aliquat 336萃取醋酸的平衡特性

选择Aliquat 336为萃取剂 ,氯仿、正辛醇和煤油为稀释剂 ,醋酸稀溶液为分离溶质 ,研究了稀释剂种类、反应剂浓度、水相 pH值、溶质在水相的浓度等因素对醋酸萃取分配系数的影响 ,分析了Aliquat 336萃取醋酸的机理 ,并在此基础上建立了描述萃取平衡的数学模型 .结果表明 :萃取结果基本符合反应剂与稀释剂的简单加和 ;稀释剂对萃取效果的影响显著 ,随Aliquat 336浓度的增大 ,氯仿和煤油为稀释剂时的萃取能力较正辛醇增加得快 ;随 pH值的变化D存在一个最大值 ,该值只与反应剂在有机相中的浓度有关 .Aliquat 336萃取醋酸存在阴离子交换和化学缔合两种机制 ,表观的阴离子交换反应平衡常数K₁在有稀释剂的条件下比纯反应剂时有所增大 ,其中氯仿的影响相对较大 ,表观的化学缔合反应平衡常数K₂ 在有稀释剂的条件下表现为 ,惰性稀释剂煤油对K₂ 的影响不明显 ,氯仿具有强化的作用 ,而正辛醇具有削弱Aliquat 336与醋酸化学缔合的能力 .     

Reactive extraction of itaconic acid using tri‐n‐butyl phosphate and aliquat 336 in sunflower oil as a non‐toxic diluent

Itaconic acid finds a place in various industrial applications. It can be produced by biocultivation in a clean and environment friendly route but recovery of the acid from the dilute stream of the bioreactor is an economic problem. Reactive extraction is a promising method to recover carboxylic acid but suffers from toxicity problems of the diluent and extractant employed. So there is need for a non‐toxic extractant and diluent or a combination of less toxic extractants in a non‐toxic diluent that can recover acid efficiently. Effect of different extractants: tri‐n‐butylphosphate (TBP) (an organophosporous compound) and Aliquat 336 (a quaternary amine) in sunflower oil was studied to find the best extractant–sunflower oil combination. Equilibrium complexation constant, K_E, values of 1.789 and 2.385 m³ kmol^?1, respectively, were obtained for itaconic acid extraction using TBP and Aliquat 336 in sunflower oil. The problem of toxicity in reactive extraction can be reduced by using a natural non‐toxic diluent (sunflower oil) with the extractant. Copyright © 2010 Society of Chemical Industry     

季铵盐(Aliquat 336)萃取对氨基苯磺酸的特性研究

利用季铵盐(Aliquat 336)为反应剂,在较宽的pH值条件下,研究了对氨基苯磺酸稀溶液的萃取相平衡特性;测定了反应剂浓度、稀释剂种类、盐的存在以及溶液pH值对反应萃取平衡分配系数的影响;提出了反应剂与对氨基苯磺酸负离子的阴离子交换反应机理,建立了平衡分配系数D值的表达式。结果表明,极性稀释剂不利于对氨基苯磺酸的萃取,惰性稀释剂能提供较大的萃取平衡分配系数,其顺序为:苯>四氯化碳>氯仿>正辛醇;盐的存在会降低Aliquat 336的萃取效率;与三烷基胺(Alamine 336)相比,Aliquat 336具有更宽的pH值适用范围。     

Reactive extraction of propionic acid using tri‐n‐octylamine,tri‐n‐butyl phosphate and aliquat 336 in sunflower oil as diluent

BACKGROUND : Propionic acid is widely used in chemical and allied industries and can be produced by biocultivation in a clean and environmentally friendly route. Recovery of the acid from the dilute stream from the bioreactor is an economic problem. Reactive extraction is a promising method of recovering the acid but suffers from toxicity problems of the solvent employed. There is thus a need for a non‐toxic solvent or a combination of less toxic extractants in a non‐toxic diluent that can recover acid efficiently. RESULTS: The effect of different extractants (tri‐n‐butylphosphate (TBP), tri‐n‐octylamine (TOA) and Aliquat 336) and their mixed binary solutions in sunflower oil diluent was studied to find the best extractant‐sunflower oil combination. Equilibrium complexation constant, K_E, values of 4.02, 3.13 and 1.87 m³ kmol^?1 were obtained for propionic acid extraction using Aliquat 336, TOA and TBP, respectively, in sunflower oil. The effect of different modifiers (1‐decanol, methylisobutyl ketone, butyl acetate and dodecanol) on the extraction was also studied and it was found that modifiers enhance extraction, with 1‐decanol found to be the best. CONCLUSION: The problem of toxicity in reactive extraction can be reduced by using a non‐toxic diluent (sunflower oil) or a modifier in a non‐toxic solvent, with the extractant. The addition of modifiers was found to improve the extraction. Copyright © 2008 Society of Chemical Industry     

Study of lactic acid extraction with higher molecular weight aliphatic amines

Lactic acid extraction was studied with two extractants, trioctyl amine (TOA) and Aliquat 336, in three diluents (methylisobutyl ketone (MIBK), octanol and paraffin liquid). The effects of organic phase extractant concentration and aqueous phase pH on the extraction process were examined. Among the extractants, TOA was found to be a better extractant than Aliquat 336 in all the diluents. In experiments with 50% (v/v) TOA in methylisobutyl ketone, 79% lactic acid could be extracted (initial lactic acid concentration 86·96 g dm⁻³). MIBK had a profound effect on the extraction behaviour of TOA in comparison with octanol and paraffin liquid while none of the diluents affected the extraction with Aliquat 336. The extraction of lactic acid was favoured at low pH. The toxicities of TOA and the diluents to Lactobacillus rhamnosus NRRL B445 were also studied. While TOA was found to be highly toxic at the molecular and the phase level, the paraffin liquid was totally non-toxic. The extraction of glucose and yeast extract by TOA and the diluents used was found to be low, which thus enables the selective extraction of lactic acid. © 1998 SCI     

The extraction of lactic acid by emulsion type of liquid membranes using alamine 336 in escaid 100

The extraction of lactic acid from aqueous solutions through an emulsion liquid membrane containing Alamine 336 as carrier was investigated. The influence of mixing speed, diluent type, surfactant concentration, extractant concentration, feed solution pH, stripping concentration, phase ratio, and feed concentration were examined. Liquid membrane consists of a diluent (n‐heptane, toluene, kerosene, Escaid 100, and Escaid 200), a surfactant (Span 80) and an extractant (Alamine 336), and Na₂CO₃ were used as a stripping solution. It is possible to extract 91% of lactic acid from aqueous solutions using Alamine 336 in Escaid 100, as an extractant and a diluent respectively.     

Parametric optimization of green synergistic reactive extraction of lactic acid using trioctylamine,Aliquat336, and butan-2-ol in sunflower oil by response surface methodology

A novel green synergistic reactive extraction technique for the removal of lactic acid (LA) from aqueous solution was explored. Response surface methodology (RSM) was applied to optimize the process variables for LA synergistic reactive extraction using a mixture of trioctylamine and Aliquat336 as extractants. During this present investigation, 2-butanol and sunflower oil were used as organic and green diluent. Systematic investigation has been carried out to obtain the optimum process conditions viz. initial LA concentration, pH of aqueous solution, extractant ratio, extractant concentration, solvent ratio, phase ratio, temperature, stirring speed, and contact time for maximizing the LA distribution coefficient (K_D) and extraction efficiency (%, η). The highest experimentally achievable LA distribution coefficient (K_D) and extraction efficiency (%) at optimized process conditions were found to be in close agreement with those predicted by numerical optimization using RSM. Thus, the results of present finding have been shown a great ability of sunflower oil as an economic and environmentally friendly green solvent for LA extraction.     

Solvent Extraction Studies of Zinc and Cadmium with Aliquat 336-S in Aqueous Chloride Solutions

Abstract

New solvent extraction systems have been developed for the extraction of zinc and cadmium from aqueous chloride solution using Aliquat 336-S dissolved in the nonpolar solvents heavy aromatic naphtha and xylene as the extractant. Moderately high concentrations of the metalions (1 mg/ml zinc and 2 mg/ml Cd) can be extracted quantitatively from acid solutions with an equal volume of 5% Aliquat 336-S solution in 15 sec. Both zinc and cadmium can be stripped from the organic phase with a series of aqueous stripping solutions. When comparing zinc and cadmium, cadmium is the easier to extract and the more difficult to strip under the same experimental conditions.     

Extraction and separation of Pt(IV)/Rh(III) from acidic chloride solutions using Aliquat 336

Extraction and separation of Pt(IV)/Rh(III) from chloride solutions using Aliquat 336 (Quaternary ammonium salt made by the methylation of mixed tri octyl/decyl amine) diluted in kerosene as an extractant/synergist alone and mixed with organophosphorous extractants as synergists/extractants were carried out from an aqueous feed containing 0.0005 mol L⁻¹ Pt(IV)/Rh(III).Variation of hydrochloric acid concentration of aqueous phase from 0.005 to 10.0 mol L⁻¹ increased the percentage extraction of platinum up to 5.0 mol L⁻¹ there after it decreases. Whereas in the case of rhodium, from 0.005 to 1.0 mol L⁻¹ acid range the percentage extraction was decreased from 1.0 to 10.0 mol L⁻¹ acid range is favorable for extraction. Platinum(IV)/rhodium(III) separation factor of 279.2 was obtained at 1.0 mol L⁻¹ HCl concentration with 0.005 mol L⁻¹ Aliquat 336 and separation factor of 612.3 was obtained at 3.0 mol L⁻¹ HCl concentration with 0.01 mol L⁻¹ Aliquat 336. The present study optimized the various experimental parameters like phase contact time, effect of extractant, salts, temperature, loading capacity of extractant, stripping studies with various mineral acids/bases, recycling and reusing capacity of extractant up to ten cycles.