Design method of extractant for liquid-liquid extraction based on elements and chemical bonds

In the petrochemical industry process, the relative volatility between the components to be separated is close to one or the azeotrope that systems are difficult to separate. Liquid-liquid extraction is a common and effective separation method, and selecting an extraction agent is the key to extraction technology research. In this paper, a design method of extractants based on elements and chemical bonds was proposed. A knowledge-based molecular design method was adopted to pre-select elements and chemical bond groups. The molecules were automatically synthesized according to specific combination rules to avoid the problem of “combination explosion” of molecules. The target properties of the extractant were set, and the extractant meeting the requirements was selected by predicting the correlation physical properties of the generated molecules. Based on the separation performance of the extractant in liquid-liquid extraction and the relative importance of each index, the fuzzy comprehensive evaluation membership function was established, the analytic hierarchy process determined the mass ratio of each index, and the consistency test results were passed. The results of case study based on quantum chemical analysis demonstrated that effective determination of extractants for the analysis of benzene-cyclohexane systems. The results unanimously prove that the method has important theoretical significance and application value.

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.

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 D2EHPA 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.

Application of NaHCO_3/ DTPA Extractant-ICP Spectrometry Technique in Soil Test for Availability of Nutrients and Heavy Metals

Soil test for availability of nutrients and heavy metals is extensively served as a means for the evaluations of soil fertility, and environmental effects and phytotoxicity of pollutants in soils, and for the fertilizer recommendation in agricultural and environmental sciences. Therefore, great attention has been paid to the measurement of elemental availability in soil test.

Separation of Indium and Iron from Dilute Sulphate Solutions with a Phosphorous Mixer Extractant

The phosphorous mixer introduced could replace D2EHPA as an extractant applied in the extraction of indium. The extraction properties of the phosphorous mixer were studied. The influences of extractant concentration, organic/aqueous (O/A) phase ratio, equilibrium time, and pH value of the feed solutions on the extraction of indium, and separation of indium-iron were investigated experimentally. Under the best operating conditions, more than 98% of indium. was extracted through two-stage counter-current extraction. The optimizing condition of indium extraction is determined as follows: O/A = 1 : (9-12) in volume ratio; 30% PPD in sulphonated kerosene; pH of the feed, about 0.6; equilibrium time, 3-5 min. The extractant has good reusing and anti-aging properties.

Recycle use of phosphorous mixer extractant to extract indium

The stripping and regeneration of the loaded organic phase of phosphorousmixer extractant (PPD) were studied. The mixed solutions (3 mol/L HCl +2 mol/L ZnC1_2) were used asthe stripping agent and more than 99 percent of indium can be stripped after three-stage strippingwhen the volume ratio of organic phase to stripping agent is 1:1. The organic phase can he recycledto use alter regeneration with HCl. The parallel contrast experiments with D_2EHPA (di-2-ethyl hexylphosphoric acid) were carried out under the same conditions. The results show that the mixerextractant has good reusability and the stripping and regeneration of PPD are superior to those ofD_2EHPA.

On the database-based strategy of candidate extractant generation for de-phenol process in coking wastewater treatment

A database-based strategy of candidate generation was proposed for molecular design of new de-phenol extractants following the idea of finding new applications of existing commercial compounds. The strategy has the advantage that the environmental, safety and health risks of candidate compounds are known and controllable. In this work, the Existing Commercial Compounds(ECC) database and special combined search strategy were developed as the base for the proposed CAMD method following such idea, and molecules for phenol extraction used in coking wastewater treatment were selected from the ECC database. The candidate solvents cover the following categories: ketones, esters, ethers, alcohols, anhydrides and benzene compounds, which are consistent with the de-phenol extractants commonly used in the industry or experiment. The compounds with higher partition coefficient and selectivity than widely used methyl isobutyl ketone(MIBK) are mainly ketones. 26 obtained molecules show higher partition coefficient and selectivity than MIBK, which are suggested to be further investigated by experiment. Furthermore, analysis of these potential molecules may present the effective functional groups as the initial group set to generate new molecular structures of de-phenol extractants. The results show that the proposed method enables us to efficiently generate chemicals with benefits of less time, less economical cost, and known environmental impact as well.

Study on the Synergistic Extraction of Ytterbium with 1－Phenyl－3－Methyl－4－（α－Furoyl）－5－Pyrazolone and Neutral Extractant

The extraction of Yb3+ by HA [1-phenyl-3-methyl-4-(α-furoyl)-5-pyrazolone] and by HA in combination with a neutral extractant B in toluene have been studied, where B represents n-butyloctyl sulfoxide (BOSO), n-pentylhexyl sulfoxide (PHSO), ethyl-n-dodecyl sulfoxide (EDSO), diphenyl sulfoxide (DPSO) or TBP. The composition of the synergistic extraction complexes have been shown to be YbA3·B and their extraction equilibrium constants have been determined separately.

DOUBLE SYNERGISTIC EFFECTS AND EXTRACTION KINETICS OF A MICELLE MIXED EXTRACTANT SYSTEM I DOUBLE(KINETIC AND THERMODYNAMIC)SYNERGISTIC EFFECTS AND EXTRACTION MECHANISMS

The equilibria and kinetic characteristics of a micelle mixed extractant system-D2 EHPA-MPA（MPA-monoalkyl phosphoric acid with long carbon chain and micellization）in extractionof the Al3+ions were studied.It was found that the system has double synergistic effects on theextraction of the Al3+ions.The compositions of the synergistic complexes were determined andthe synergistic reaction equations were obtained.

Linear Free Energy Relationships in Extraction of Rare Earths by Acidic Organophosphorus Extractants

The correlation relationships of apparent extraction equilibrium constant (1gK(ex)) with the electronic effect parameter( Sigma sigma(Phi)) and the steric effect parameter ( Sigma upsilon ) of the substituents in extractant molecules are investigated by linear regression analysis in the extraction of rare earths by various classes and structures of monoacidic organophosphorus extractants. The results indicate that in Linear free energy relationship formula 1gK(ex) = rho Sigma sigma(Phi) + psi Sigma upsilon + h generally follows for this kind of extraction systems. Accordingly, the quantitative structure-behaviour relationships of extractants are discussed. These relationships can be preliminarily applied to predict the 1gK(ex) values of rare earth extraction with definite structures of this class of extractants, and thus can provide some directions for the design of new RE extractants.

Influence of copper solvent extractant on microbial community structure of acidophilic microorganisms

The influence of different concentrations of copper solvent extractant ZJ 988 on the growth and activity of acidophilic microorganisms was studied and the microbial community structures were compared by 16S rRNA gene clone library analysis.The total bacteria numbers are reduced when 0.5%(volume fraction) extractant is added.The proportions of Acidithiobacillus ferrooxidans and Acidiphilium organovorum are increased,whereas the proportion of Leptospirillum ferriphilum is reduced.When the concentration of extractant is elevated to 1%,growth of all bacteria is inhibited.Clone library results reveal that the dominant bacteria in the culture solution with/without the extractant are At.ferrooxidans,A.organovorum and L.ferriphilum.The sensitivity order of the three bacteria to the extractant from the most to the least is found to be L.ferriphilum>At.ferrooxidans>A.organovorum.

Quantum Chemical Calculation on the Structures and Electronic Properties of Phosphonate Ester as Rare Earth Extractants

Molecular mechanics, molecular dynamics and semi empirical quantum chemical method have been used to study the geometric and electronic structures of six phosphonate ester as rare earth extractants. The results show that the phosphorus atom exhibits sp 3 hybridization. The structures of the extractants are determined by the repulsion of the hydrocarbon groups. In the extractants that have two 2 ethyl hexyl groups, one 2 ethyl hexyl extends straight, and the other extends twistily. When the number of oxygen atom decreases, the negative charge of the phosphoryl oxygen atom increases, but the negative charge of oxygen atom and the positive charge of hydrogen of the hydroxyl group decreases, and the energies of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital(LUMO) increase. The energies of the occupied frontier orbitals are close to each other.

Influence of Modifiers, Extractants, and Trappers on Lipid Composition with Liquids in Standard State Extraction, Supercritical Fluid Extraction and Trapping by Supercritical Fluid Extraction, Part II

Modifiers have a broad array of influences on extraction with liquids in standard state, supercritical fluid extraction (SFE), trapping by SFE and supercritical fluid chromatography (SFC). They can significantly change the qualitative and quantitative results. Quantitative and qualitative results can be influenced by different extractants and modifiers in different ways as it was shown by Brondz et al. at 2007 in “The real nature of the indole alkaloids in Cortinarius infractus: Evaluation of artifact formation through solvent extraction method development”, J. Chromatography A, 1148, 1-7. The choice of correct extractant, modifier, and trapper to the bulk mobile phase for supercritical fluids (SFs) or for liquids in subcritical or in the liquids in standard state is a challenge in any extraction procedure. This is the second paper in a sequence that describes the influence of extractants and modifiers on the performance of SFs and results of extraction with liquids in standard state and SFE. Here, attention is given to possible mistakes in qualitative and quantitative results by poor understanding of the influence of extractants, modifiers, and trappers on extraction and trapping process by a careless choice of extractant, modifier, and trapper for extraction with liquids in standard state and SFE. The SF chosen for discussion in the paper is CO2. However, similar effects can be observed with use of other SFs and fluids in subcritical and standard states. In this paper, the discussion of lipids, fatty and carboxylic acids have been chosen as target analytes for extraction, trapping and analysis. Some examples from extraction with liquids in the standard state and trapping in the supercritical state (collection) have been furnished with the wrong extractant, modifier, or trapper which is presented for illustration of inappropriate choice of extractants, modifiers, and trappers.

Monoalkyl Esters of Isoalkylphosphonic Acid as Extractants in Rare Earth Separation

Four monoalkyl esters of isoalkylphosphonic acids have been studied for the chromatographic separation of rare earths (RE).The relationship between distribution ratios and acid concentration of the eluants for samarium and ytterbium has been explored.The characteristics of these extractants loaded onto macroreticular poly (methyl methacrylate) resin beads for the separation of lanthanum,cerium,praseodymium and neodymium have been compared.Among the extractants studied,mono(1-methylheptyl) ester of isooctylphosphonic acid was found to be the best for RE separation.The acidity for separation is lower than any known P-containing extractants for the same purpose.For instance,with 1.73 mol·L^(-1) nitric acid as eluent,thulium,ytterbium and lutetium can be separated quantitatively.The extractant-loaded resins possess high column efficiency with good kinetic characteristics.The extraction mechanism was also explored.

Effect of Extractant and Temperature on Phenolic Compounds and Antioxidant Activity of Selected Spices

Ten spices marketed in Jordan, (Syzygium aromaticum L., Coriadrum sativum L., Cuminum cyminum L.,Zingiber officinale Rosc., Elettaria cardamomum, Curcuma longa, Rhus coriaria L., Cinnamomum zeylanicum Blume, Foeniculum vulgare Mill and Laurus nobilis L.) were investigated for their phenolic compounds and antioxidant activity. The influence of different extractants (methanol, ethanol and acetone) at different temperatures (20, 40 and 60°C) was examined. Results showed at 60°C using methanol, cloves had the highest level of total phenolics (781.0 mg GAE/100g using acetone). At 40°C, sumac and cloves had the highest amounts of total phenolics (343.9 mg/100g and 342 mg GAE/100g respectively). At 20°C, cloves continued to have the highest amount of total phenolics (394.7 mg/100g) using methanol as extactant. Ethanol as extractant, cloves gave the highest level of phenolics (548 mg GAE/100g, 493.4 mg GAE/100g) at 60°C, while at 20°C cloves and sumac showed the highest concentrations of phenolics (350.8 mg GAE/100g and 342.8 mg GAE/100g respectively). Acetone as extractant at 60°C, cloves had the highest levels of phenolics (781 mg GAE/100g) while at 40°C and at 20°C, sumac contributed the highest levels of total phenolics (583.2 mg GAE/100g and 754.5 mg GAE/100g). The total phenolics concentration varied significantly among the spices. Their values varied according to the extractant and extracting temperature. IC50 (radical scavenging activity) reflecting the antioxidant activity was presented. Results showed that cloves had the highest antioxidant activity while the cinnamon, turmeric and sumac had a appreciable level of antioxidant activity. Green cardamom and coriander had the lowest antioxidant activity. Antioxidant activity was positively correlated with total phenolic compounds content of the investigated spices.

Evaluation and Comparison of DTPA Extractanting Methods for Available Cationic Micronutrients in Non-acidic Soils of Andhra Pradesh,India

The research work was carried out to compare and evaluate the extractability of cationic micronutrients(Zn,Cu,Fe and Mn)using widely employed diethylene triamine pentaacetic acid(DTPA)-triethanolamine(TEA)-CaCl2 method with that of multinutrient extractant(ammonium bicarbonate(AB)-DTPA)in Inceptisols,Alfisols and Entisols in the erstwhile united Andhra Pradesh.The percent variation of extraction of Zn was higher in soils with DTPA-TEA-CaCl2 over AB-DTPA method in all the soil orders(types)in the range of 35.3% to 46.2%.AB-DTPA extracted high amounts of Cu to an extent of 10%-21% in Entisols and Alfisls,respectively.In Inceptisols both extracatants extracted equal amounts of Cu.AB-DTPA extracted high amounts of Fe 13% and 18% in Alfisols and Entisols compared to that of DTPA-TEA-CaCl2 method and DTPA-TEA-CaCl2 method was good extract for Fe in Inceptisols and even for Mn in Alfisols.The amounts of micronutrient contents extracted were found to be highly and significantly correlated with soil properties like electrical conductivity(EC)and organic carbon(OC).The individual micronutrient contents of Zn,Cu and Fe extracted by DTPA-TEA-CaCl2 methods were found to be highly correlated with that of AB-DTPA extractant.However,such correlation was not observed for Mn extraction when all soils were grouped.

Relationship between Pectic Substances and Strand Separation of Cooked Spaghetti Squash--Part 2. Changes in Firmness, Histological Structure and Pectic Substances during Soaking in Pectin Extractants

The flesh of spaghetti squash separates into strands when cooked. The purpose of this paper is to investigate the cause of strand separation （during cooking） by soaking for 24 h at 35 ℃ in solutions with three kinds of pectin extractant. The changes in strand separation, firmness, histological structure and the pectin of flesh during soaking in 0.01 N HCI solution （pH 2.0）, 0.035 M ammonium oxalate solution （pH 4.0） or 2% sodium hexametaphosphate solution （pH 4.0） were investigated. When flesh was soaked in the HCI solution, the separation into strands and removal of calcium and magnesium were greater than that soaked in other pectin extractants. High methoxyl pectin was extracted by soaking in HC1 solution （pH 2.0） due to removal of polyvalent cations. This result shows that high methoxyl pectin glues strands together in the flesh of spaghetti squash. The shape of the cells which constituted strands was round; on the other hand, that of cells surrounded strands was elongated. When cooked in boiling water or soaked at pH 2.0, the shape of the former cells was maintained, but the latter cells, which contributed to adhesion between strands, broke down. Thus, the flesh separated into strands. When flesh was boiled for 15-30 min, pectin degraded and dissolved in the cooking solution; consequently, the flesh separated into strands and also the middle lamella of cell walls of strands separated. However, pectin remaining in strands maintained their crispness.

Comparative Study on the Effect of Extractant on the Detection of Imidaclothiz Residue in Tea

Imidaclothiz residue in tea was determined by high performance liquid chromatography（ HPLC）,using different extractants including hexane,acetonitrile,acetone,hexane-acetonitrile（ 1∶ 1）,acetonitrile-acetone（ 1∶ 1） and hexane-ethyl acetate（ 1∶ 1）. The results indicated that all the extractants displayed excellent extraction capacities of imidaclothiz residue in tea and insignificant interference on the accuracy. Under the optimized extraction volume（ 20 ml）,the recovery values were in the ranges of 82. 3%-100. 7%,85. 8%-101. 1%,85. 9%-95. 2%,82. 3%-101. 3%,82. 4%-100. 5% and 88. 6%-102. 3%,respectively,with the relative standard deviations smaller than 10%. Moreover,mixed solvent showed improved extraction capacity,and the highest extraction capacity and promoted stability were approached by using hexane-ethyl acetate（ 1∶ 1） as coextractants.

Redistribution of Pb, Zn and Cu Fractions in Tailing Soils Treated with Different Extractants

The efficiency of EDTA, HNO3 and CaCl2 as extractants to remove Pb, Zn and Cu from tailing soils without varying soil pH was investigated with distributions of Pb, Zn and Cu being determined before and after extraction using the sequential extraction procedure of the optimized European Community Bureau of Reference (BCR). Results indicated that EDTA and HNO3 were both effective extracting agents.The extractability of extractants for Pb and Zn was in the order EDTA > HNO3 > CaCl2, while for Cu it was HNO3 > EDTA > CaCl2. After EDTA extraction, the proportion of Pb, Zn and Cu in the four fractions varied greatly, which was related to the strong extraction and complexation ability. Before and after extraction with HNO3 and CaCl2, the percentages of Pb, Zn and Cu in the reducible, oxidizable and residual fractions changed little compared to the acid-extractable fraction. The lability of metal in the soil and the kinds of extractants were the factors controlling the effects of metal extraction.

Distribution Coefficient of Caprolactam and Methyl Caprolactam Using Benzene or Toluene as Extractants： Experiments and Prediction

To get high purity caprolactam is a challenging task in the chemical fiber industry. To date, reports on the prediction of the distribution of caprolactam and its derivative chemicals have been few. In this study, the extraction of caprolactam with toluene as the extractant and N-methyl caprolactam with benzene and toluene as theextractants has been camed out. By defining new UNIFAC groups and calibrating related interaction parameters, aUNIFAC method was introduced to predict the equilibrium concentration of caprolactam and methyl caprolactam intoluene or benzene extraction processes. The calculated results fit very well With the experimental data. Using theUNIFAC model, the selectivity of extractants can be predicted.