烷基膦酸类萃取剂与喹啉类萃取剂N_(601)协萃锗(Ⅳ)的研究

研究了盐析剂浓度和水相ｐＨ值对分配比Ｄ的影响。研究了烷基膦酸萃取剂Ｐ５０７和喹啉类萃取剂Ｎ６０１协萃锗的机理，并对萃取平衡常数和热效应进行了估算。

Kinetics of cerium(Ⅳ) and fluoride extraction from sulfuric solutions using bifunctional ionic liquid extractant(Bif-ILE)[A336][P204]

The extraction kinetics of Ce（Ⅳ） and Ce（Ⅳ）-F^- mixture systems from sulfuric solutions to n-heptane solution containing Bif-ILE[A336][P204]（[trialkylmethylammonium][di-2-ethylhewanxylphosphinate]） with a constant interfacial area cell with laminar flow were studied,just to elucidate the extraction mechanism and the mass transfer models.The data were analyzed in terms of pseudo-first-order constants.The effects of stirring speed,specific interfacial area and temperature on the extraction rate in both systems were discussed,suggesting that the extractions were mixed bulk phases-interfacial control process.Supported by the experimental data,the corresponding rate equations for Ce（Ⅳ） extraction system and Ce（Ⅳ）-F^- mixture extraction system were obtained.The experimental results indicated the rate-controlling step.The kinetics model was deduced from the rate-controlling step and consistent with the rate equation.

Thermodynamics and mechanism of vanadium(IV) extraction from sulphate medium with D2EHPA,EHEHPA and CYANEX 272 in kerosene

Extraction of vanadium（IV） from sulphate acid solution was studied using organophosphorous-based extractants D2EHPA, EHEHPA and CYANEX 272 in kerosene. The different parameters affecting the extraction of vanadium（IV） under equilibrium conditions were separately investigated to elucidate the stoichiometry of the extracted species. The distribution ratio of vanadium increased with increasing equilibrium pH of the aqueous phase, concentration of the extractants and temperature. D2EHPA was found to be a stronger extractant, having greater pH functionality than EHEHPA and CYANEX 272. Extraction of vanadium（IV） by these organophosphorous-based extractants involved cation exchange mechanism, and the extracted species appear to be VOR2（HR）2 in the low equilibrium pH and VOR2 in the higher equilibrium pH, where HR refers to the three acidic extractants.

Removal of chromium(Ⅲ) from aqueous waste solution by predispersed solvent extraction

The extraction experiments of chromium（W） from aqueous waste solution by predispersed solvent extraction （PDSE） process with extractant （HEHPEHE） and its mixture, including acidic extractant （D2EHPA）, alkaline extractant （TOA） and neutral extractant （TBP） were carried out respectively. It is found that the extractant HEHPEHE exhibited high extraction selectivity to chromium（III） from aqueous waste solution. The colloidal liquid aphrons （CLAs） were successfully generated using kerosene as a solvent, HEHPEHE as an extractant, sodium dodecyl benzene sulphate （SDBS） as a surfactant in aqueous phase and polyoxyethylene sorbitol anhydride monolaurate （Tween-20） in oil phase. To study the extraction efficiency and advantages of the PDSE process in the removal of chromium（III）, the effects of major factors, such as initial chromium（III） concentration, volume of colloidal gas aphrons （CGAs）, HEHPEHE volume fraction, phase ratio （solvent phase to water phase）, mass fraction of dodecyl trimethylammonium bromide （HTAB）, mass fraction of SDBS, mass fraction of Tween-20 and initial pH of aqueous waste solution were also investigated and the appropriate process conditions were obtained. Under the appropriate conditions, the extraction efficiency of chromium（III） above 99.9 % can be achieved and the treated aqueous waste solution can be discharged directly without polluting the environment.

Preparation and in Vitro Evaluation of Polylactic Acid (PLA) or Polylactic-co-Glycolic Acid (PLGA) Microcapsules Loaded with Estradiol

Aim PLA/PLGA was used as biodegradable and biocompatible carriers to achieve sustained release of estradiol (E 2). Methods Microcapsules (MC) were prepared by an emulsification solvent extraction method, and then the properties and in vitro drug release behavior of MC were examined. An analysis of variance (ANOVA) was used to test the statistical significance. Then, multiple comparisons were made with a T method between levels to examine the significance of difference further. For all the results a P value 】0 05 was considered statistically insignificant . Results Under the same conditions, the water adding speed and the particle size had significant effects ( P 【0 01) on the entrapment efficiency of MC; the water adding speed and the concentration of PLA in the oil phase had significant effects ( P 【0 01) on the diameter MC in medium. Release of E 2 from MC was influenced significantly ( P 【0 01) by the water adding speed and the type and molecule weight of the polymers. But the differences between levels of the variates were not all significant. Conclusion E 2 PLA/PLGA MC with various properties can be formed when the formulation and the technology were changed accordingly.

Determination of Eleutheroside B and E in Acanthopanax Preparations by High-P erformance Liquid Chromatography with Solid-Phase Extraction

Aim An HPLC method for analyzing eleutheroside B (ELU B) and eleutheroside E(ELU E) , two of the main active substances of Acanthopanax preparations were studied. Methods Thesamples were analyzed on a kromasil ODS column with water-acetonitrile as a gradient mobile phase.The flow rate was 0.8 mL·min^(-1) and detecting wavelengths were 206 nm for ELU B, 220 nm for ELUE, solid phase extraction (SPE) and internal standard-salicin were selected. Results The recoveriesof Acanthopanax tablets and injection were 90.4% - 96.8% and 96.4% - 99.8% for ELU B, 87.7% -93.3%and 95.7% - 98.5% for ELU E, respectively. The linear ranges were 4.45 - 22.25 μg· mL^(-1) (r =0.999 8) and 5.11 - 25.55 μg·mL^(-1) ( r = 0.999 7) respectively. Conclusion This method can savethe time for cleaning the chromatographic system and improve sensitivity for Acanthopanaxpreparations , thus providing a way to evaluate the quality of Acanthopanax preparations.

Recovery of cobalt and nickel in the presence of magnesium and calcium from sulfate solutions by Versatic 10 and mixtures of Versatic 10 and Cyanex 301

The extraction and stripping characteristics of Versatic 10 and its mixtures with Cyanex 301 were investigated for the recovery of cobalt and nickel from sulfate solutions containing magnesium and calcium. The optimum extraction factors of Versatic 10 were initial pH of 2.5, O/A ratio of 1/3, and saponification rate of 60%. The loaded Versatic 10 was stripped by using 2 mol/L H2SO4 at O/A ratio of 1/1. The optimum volume ratio of Versatic 10 to Cyanex301 was 7/3 in the mixtures, which could effectively reduce the equilibrium pH to 3.50. And the loaded mixtures were stripped by using 2 mol/L H2SO4at O/A ratio of 1/2. The reaction principle of Versatic10 and metal ions is an ion exchange reaction. However, in the extraction reaction of and metal ions, besides the ion exchange reaction, the strong coordination effect between Cyanex 301 and metal ions also exists, which is much weakened in the extraction reaction of the mixtures and metal ions.

Recovery of Copper（II） and Nickel（II） from Plating Wastewater by Solvent Extraction

The solvent extraction technology, was applied to recover Cu^2＋ and Ni^2＋ from plating wastewater.Lix984N was chosen as the extractant due to-its gooff extraction performance. The influence parame-ters were examlned. The results show that the separation of Cu^2＋ and Ni＂ from sulphate medium can be realized by adjusting pH value with the help of Lix984N. For extracting Cu^2＋ and Ni^2＋, the optimal pH values are 4 and 10.5, and the maximal extraction percentages are 92.9% and 93.0%, respectively .With recovered Cu^2＋ and Ni^2＋ stripped in 170g.L^ -1 and 200 g.L^-1 H2SO4 medium, the stripping percentages of Cu^2＋ and Ni^2＋ are 92.9% and 93.0%, respectively. This method is simple and can be used to recover Cu^2＋ and Ni^2＋ from plating wastewater. And a flow sheet for separation of Cu^2＋ and Ni^2＋ is presented.

Recovery of nickel,cobalt,copper and zinc in sulphate and chloride solutions using synergistic solvent extraction

A number of synergistic solvent extraction （SSX） systems have been developed to recover nickel, cobalt, zinc and copper from sulphuric and chloride leach solutions by the solvent extraction team of CSIRO, Australia. These in- clude （1） Versatic 10/CLXS0 system for the separation of Ni from Ca in sulphate solutions, （2） Versatic 10/4PC system for the separation of Ni and Co from Mn/Mg/Ca in sulphate solutions, （3） Cyanex 471X/HRJ-4277 system for the separation of Zn from Cd in sulphate solutions, （4） Versatic 10/LIX63 system for the separation of Co from Mn/Mg/Ca in sulphate solutions, （5） Versatic 10/LIX63/TBP system for separation of Ni and Co from Mn/Mg/Ca in sulphate solutions, （6） Versatic 10/LIX63 system for the separation of cobalt from nickel in sulphate solutions by difference in kinetics, （7） Cyanex 272/LIX84 system for the separation of Cu/Fe/Zn from Ni/Co in sulphate solutions, （8） Versatic 10/LIX63fFBP system to recover Cu/Ni from strong chloride solutions, and [9） Versatic 10/LIX63 system to separate Cu from Fe in strong chloride solutions. The synergistic effect on metal separation and efficiency is presented and possible industrial applications are demonstrated. The chemical stability of selected SSX systems is also reported.

Recovery of iron and rare earth elements from red mud through an acid leaching-stepwise extraction approach

A feasible approach to selectively recover iron and rare earth elements(REEs)from red mud through acid leaching-coordination-solvent extraction was proposed.The leaching efficiencies of Fe,Al,Ti,Sc,La,Ce,Nd and Y can reach up to 95.9%,82.1%,68.3%,93.3%,82.3%,96.9%,98.3%and 95.6%,respectively,under the optimal condition in the leaching process.Aliquat 336 showed excellent extraction performance of iron in chloride-rich solution,and the maximum extraction efficiency can reach over 96%in one time extraction while the loss of other metals was less than 10%,under the condition of Aliquat 336 concentration(v/v)of 30%,aqueous-organic ratio of 1.0 and extraction time of 20 min.Furthermore,P204 can effectively extract the scandium while Al and most other REEs remain in the aqueous phase.This approach may provide a new insight for the recovery of valuable resources from red mud.

Selection and Evaluation of a New Extractant for Caprolactam Extraction

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.

Mass Transfer of Copper（Ⅱ） in Hollow Fiber Renewal Liquid Membrane with Different Carriers

The extraction ability of organophosphorus extractant D2EHPA(di-2-ethylhexyl phosphoric acid) and hydroximic extractant Lix984N are investigated by the extraction equilibrium experiments.Effects of carrier concen-tration and organic/aqueous volume ratio on the mass transfer of hollow fiber renewal liquid membrane(HFRLM) are studied.Results show that,in the extracting process,kerosene and n-heptane are more suitable than methyl-isobutyl ketone,butylacetate and benzene as the diluents of D2EHPA or Lix984N.The favorable feed pH is 4.4 for D2EHPA and 2.6 for Lix984N.The mass transfer flux of HFRLM increases with carrier concentration and finally reaches a plateau.The mass transfer flux and the overall transfer coefficient increase with the organic/aqueous volume ratio,reach the maximum and then decrease.

Extraction and stripping of Cu and Ni from synthetic and industrial solutions of Sarcheshmeh Copper Mine containing Cu, Ni, Fe and Zn ions

The extraction and stripping of Cu and Ni ions from synthetic and industrial solutions of Sarcheshmeh Copper Mine containing Cu(770 mg/L),Ni(3200 mg/L),Fe(800 mg/L)and Zn(200 mg/L)were comprehensively investigated using D2 EHPA,LIX 984,Cyanex 302,Chemorex CP 150 and Acorga 5774 diluted in kerosene.The influential parameters such as mixing speed and time,concentration of extractant,p H and temperature were considered in extraction stage.Furthermore,stripping of Cu and Ni was examined using different inorganic and organic acids(sulfuric,hydrochloric,nitric and citric acids)with different concentrations.The results indicated that the highest extractions of Cu and Ni occurred within 3 min,with the mixing speed of 500 r/min,28℃and A/O ratio of 1:1.Moreover,Cu was extracted by LIX 984 at the concentration of 10%(v/v),whereas Ni was extracted by Cyanex 302 at the concentration of 30%(v/v),efficiently.The optimal p H for Cu and Ni extraction is in ranges of 2-3 and 4-5,respectively.Cu and Ni were selectively extracted with the recoveries of 85%,93%and 77%,82%from synthetic and industrial solutions containing Ni,Cu,Zn and Fe ions,respectively.The results of optimal condition showed that 96%of Ni and 93%of Cu were stripped from the synthetic and industrial solutions.Finally,four elements Zn,Fe,Cu and Ni were extracted in three stages with D2 EHPA,LIX 984 and Cyanex 302 extractants respectively with the least impurities.

Study on microwave-assisted extraction of coal

The effect of different factors on coal extraction yield-temperature, solvent, coal type and irradiation time were investigated for different China coals under microwave-assisted extraction（MAE）. The results show that the optimum temperature for ethanol, acetone and THF are 393,373 and 373 K respectively and the extraction yield of THF is higher than that of other two solvents under MAE. Extraction with several single organic solvents were conducted for the 5 typical China coals-Shenfu, Tongchuan, Panzhihua, Yitai and Huating coal under microwave-assisted extraction and Soxhlet extraction. Results indicat that extraction yield of ethylenediamine, ethanol, acetone, tetrahydrofuran under MAE are all higher than that of Soxhlet extraction and MAE required less time. Tongchuan coal extracts of ethanol and acetone which were extracted by MAE and Soxhlet extraction were analyzed by GC/MS.

Extraction kinetics of zinc by new extractant in ammoniacal system

The controlling step and the extraction reaction rate equation of zinc extraction from Zn（II）-NH3 solution by using a newly synthesized organic compound, 2-acetyl-3-oxo-dithiobutyric acid-myristyl ester as the zinc extractant, were clarified. The effects of agitation speed, specific interfacial area, temperature, extractant concentration and Zn ion concentration on the extraction rate are studied in constant interfacial area cell. The results show that the extraction rate depends on interfacial chemical reaction and diffusion by using this new extraetant to extract zinc, and the apparent activation energy of this extraction reaction is measured as 28.2 kJ/mol, which demonstrates that the extraction reaction is controlled by the mixed-controlled reaction rate. The apparent reaction orders a and b are measured as 1 and 0.38, and the constant k0 is 138.70. So, when extraction conditions are controlled as [HR]=20%-50%, T=0-30℃, N=120-177 r/min and S=72.6-127.5 m-1, the solvent extraction reaction rate can be depicted as v/（mol . m-2 . s-1 ） = 138.7. exp（ - 28 206/8.314T ）. [Zn 2＋ ]r ·[HR ]o0.38.

Study on the method of recovering and separating indium from residue containing indium

A method of recovering indium from complex smelting residue containing indium was investiga ted. Indium was extracted by technique of low acid leaching and solvent extraction. The conditions of separating iron and indium were studied and the optimal conditions were determined. When the residue is two class countercurrent leached with 2 mol/L H 2SO 4 and 30 40 g/L NaCl at 100 ℃, the leaching rate of indium is 80%. The extraction rate of indium is over 98% and that of iron is less than 5% after it is third class countercurrent extracted by P204, and when sulfonated kerosene is used as solvent, acidity in aqueous phase remains the same as that of leaching liquid, and phase is for 1∶3. Using 2 mol/L HCl as back extraction agent, with phase ratio being 5∶1, by third class countercurrent back extraction, the back extraction rate of indium is over 99%, but that of iron is very low, which can meet the need of separating indium and iron.

Treatment of Sebacic Acid Industrial Wastewater by Extraction Process Using Castor Oil Acid as Extractant

Wastewater containing high concentrations of phenol and sodium sulfate is generated in sebacic acid （SA） industry. Castor oil acid, a raw material for producing SA, can be used to extract phenol from wastewater in order to reduce the amount of phenol used in the process and discharge of phenol. The results show that the extrac- tion mechanism is that hydroxyl group of phenol is linked to carboxyl group of castor oil acid by hydrogen bond. The extraction process approaches equilibrium in 30 min. Extraction ratio increases with the increase of sodium sulfate and castor oil acid, and decreases as phenol increases. When the oil-water ratio is 1 ： 3, the optimal distribu- tion coefficient of 40 is obtained. Phenol saturation concentration in castor oil acid is 1.03 mol.L-1 after extraction for 4 times. The equilibrium constant （Kex） at 25℃ is 8.41 and the endothermic enthalpy （AH） is 1.513 kJ.mo1-1. The Gibbs free energy （AG） is -5.277 kJ. tool-1 and the value of AS is calculated to be 22.3 J. mo1-1. K-1.

Copper solvent extraction from alkaline cyanide solution with guanidine extractant LIX 7950

The use of the guanidine extractant LIX 7950 extracting copper and cyanide from alkaline cyanide solution was investigated.The extraction of copper and cyanide under different initial copper and extractant concentrations was examined and the stoichiometric extraction constant of Cu(CN)32- with LIX 7950 was calculated.Both the distribution coefficient and the stoichiometric extraction constant of Cu(CN)3 2-with LIX 7950 decrease when the temperature is varied from 25℃to 45℃, indicating the extraction process is exothermic.The calculated enthalpy change of the reaction(-HΘ)is about-190 kJ/mol.The copper extraction isotherms under different molar ratios of cyanide to copper are established.The preferential extraction of Cu(CN)32- over Cu(CN)4 3-and CN -has been confirmed and a high cyanide-to-copper molar ratio tends to suppress copper loading. The loaded copper and cyanide can be stripped efficiently by the moderately strong NaOH solutions(0.5-1.0 mol/L)and the presence of NaCN in the stripping solution facilitates copper stripping.

Solvent extraction mechanism and precipitation stripping of bismuth(Ⅲ) in hydrochloric acid medium by tributyl phosphate

Tributyl phosphate(TBP) was employed for the Bi(Ⅲ) extraction from hydrochloric acid medium.The effects of extraction time and material concentration were examined.The replacement mechanism between the anion(Cl^-) and TBP was proposed for extraction.The results show the species extracted into the organic phase were found to be mainly BiCl_3·x TBP(x=2 or 3).Thermodynamic parameters of the extraction reaction were obtained from the thermodynamics analysis,which illustrates that higher temperatures show a negative effect on the extraction.Extraction isotherm was obtained with 2.16 mol/L TBP for a typical solution containing 0.1 mol/L of bismuth and 1.0 mol/L of hydrochloric acid.About 98.5 % of bismuth has been extracted from the leaching solution under the optimum condition.Moreover,oxalate was explored as a precipitation stripping agent for BiCl_3·x TBP(x=2 or 3) complexes,by which Bi(Ⅲ) was stripped in the form of Bi_2(C_2O_4)_3·7H_2O.A stripping efficiency of 99.3% was obtained in only one stage at the phase ratio of 1 and TBP also could be recycled.Therefore,the method is an efficient,effective and highly selective approach to extract Bi(Ⅲ) and to recover metal bismuth.

Solvent extraction of copper and zinc from bioleaching solutions with LIX984 and D2EHPA

The solvent extraction of copper and zinc from the bioleaching solutions of low-grade sulfide ores with LIX984 and D2EHPA was investigated. The influences of extractant content, aqueous pH value, phase ratio and (equilibration) time on metals extraction were studied. The results show that LIX984 has a higher selectivity for copper than for iron, zinc and other metals, and has the copper extraction rate above 97%, while the zinc and iron extraction rate is less than 1.6% respectively. Zinc extraction is carried out following the copper extraction from the raffinate. The zinc extraction with di(2-ethylhexyl) phosphoric acid(D2EHPA) is low due to its poor cation exchange. A sodium salt of D2EHPA is used and the zinc extraction rate is enhanced to above 98%. Though iron (Ⅲ) is strongly extracted before the extraction of zinc by D2EHPA, it is difficult to strip iron from the organic phase by sulfuric acid. The zinc stripping rate is above 99% with 100g/L sulfuric acid, while that of iron is 0.16%. Hence, the separation of zinc from iron can be achieved by the selective stripping.