Removal of arsenic(III) and arsenic(V) from sulfuric acid solution by liquid–liquid extraction

Extraction of arsenic(III) and arsenic(V) from sulfuric acid solution was studied. Cyanex^® 923, Cyanex^® 925, dialkyldithiophosphinic acids (Cyanex^® 301), hydrophobic glycol (2‐ethylhexane‐1,3‐diol), and hydroxamic acids were used as extractants. The efficiency of extraction depended on extractant, diluent, valency of arsenic, and sulfuric acid concentration. Acidic reagents extracted As(III) better than As(V), while the opposite order of extraction efficiency was observed for the solvating extractants. The use of an aromatic diluent (toluene) was preferred. Toluene was found to be a better diluent for the Cyanex^® 923 and Cyanex^® 925 than Exxsol D 220/230 and octane. In the case of neo‐decanohydroxamic acids, the type of diluent had no significant effect on extraction of arsenic. The extraction of both As(III) and As(V) increased when the concentration of the sulfuric acid in the feed increased. The co‐extraction of sulfuric acid was observed. The extraction with hydroxamic acids was significantly slower in comparison to the extraction with other reagents. Extractant: arsenic species: sulfuric acid molar ratios were determined and they confirmed the composition of extracted species. Copyright © 2003 Society of Chemical Industry     

Recovery of carboxylic acids C1?C3 with organophosphine oxide solvating extractants

This study was aimed at examining the use of the organophosphine oxides Cyanex^®921 and Cyanex^®923 for the extraction of formic, acetic and propionic acids from aqueous solutions. The stripping of monocarboxylic acids with water from the loaded extractants was also examined. The studies were aimed at determining the equilibrium conditions for extraction and stripping. Overall, the effect of the kind of extractant was not significant although Cyanex^®921 extracted carboxylic acids slightly better than Cyanex^®923 with 1:1 complexes being formed by both extractants with the acids during extraction. The efficiency of extraction depended on temperature, acid concentration and solvent, with toluene a better diluent for the extractants than octane or Exxsol^®D 220/230. Extraction efficiency increased as the concentration of acid in the feed decreased and, also, as the temperature increased, the amount of acid extracted decreased. The extraction and stripping isotherms were determined. The apparent enthalpy and entropy of the extraction reaction were determined. Distribution data for the transfer of carboxylic acids from aqueous (NaCl) solutions to organic solvents in the presence of trialkylphosphine oxide were determined at 293 K with the distribution ratios increasing as the concentration of NaCl increased. Copyright © 2005 Society of Chemical Industry     

Extraction and pertraction of phenol through bulk liquid membranes

The extraction and pertraction of phenol through a bulk liquid membrane (BLM) with Cyanex^® 923, Amberlite^® LA‐2 and trioctylamine (TOA) as carriers were studied. Cyanex^® 923 was selected as the best carrier for pertraction. The distribution coefficient of phenol for solvents with carrier and pure n‐alkanes, the individual mass‐transfer coefficient at the extraction interface and the initial flux of phenol through the extraction interface (J_Fo) decreased in the order: Cyanex^® 923 > Amberlite^® LA‐2 > TOA ? pure n‐alkanes. The opposite order was observed for the value of the mass‐transfer coefficient in BLM and the maximum flux of phenol through the stripping interface (J_Rmax). At constant driving forces the maximum fluxes through the extraction and stripping interfaces were similar when amine carriers were used. However, J_Rmax was lower than J_Fo for Cyanex^® 923. Although the kinetics of stripping was the rate‐determining step, the flux of phenol was significantly higher than in pertraction with amine carriers. The adsorption of the carrier at aqueous phase/membrane interfaces was probably responsible for the rapid and slow transfer of phenol through the extraction and stripping interface, respectively. Copyright © 2004 Society of Chemical Industry     

EVALUATION OF EXTRACTANT-COATED FERROMAGNETIC MICROPARTICLES FOR THE RECOVERY OF HAZARDOUS METALS FROM WASTE SOLUTION

ABSTRACT

A magnetically assisted chemical separation (MACS) process developed at Argonne National Laboratory is a compact method for the extraction of transuranic (TRU) metals from, and volume reduction of, liquid waste streams that exist at many DOE sites. The MACS process utilized the selectivity afforded by solvent extractant/ion-exchange materials in conjunction with magnetic separation to provide a more efficient chemical separation. Recently, the principle of the MACS process has been extended to the evaluation of acidic organophosphorus extractants for hazardous metal recovery from waste solutions. Moreover, process scale-up design issues were addressed in respect to particle filtration and recovery.

Two acidic organophosphorus compounds have been investigated for hazardous metal recovery, bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex® 272) and bis(2,4,4-trimethylpentyl) dithiophosphinic acid (Cyanex® 301). These extractants coated onto magnetic microparticles demonstrated superior recovery of hazardous metals from solution as compared with data from solvent extraction experiments. The results illustrate the possibility for diverse applications of this technology for dilute waste streams. Preliminary process scale-up experiments with a high-gradient magnetic separator at Oak Ridge National Laboratory revealed the potential for very low microparticle loss rates.     

Enrichment of salmon oil with n‐3 PUFA by lipolysis,filtration and enzymatic re‐esterification

Selective enzymatic hydrolysis of salmon oil extracted without solvent from by‐products was carried out under mild conditions, using a stereospecific sn‐1, sn‐3 lipase Novozyme^®. A modification of the lipid class composition was obtained by controlling the degree of hydrolysis (40%, 24 h). The mixture of acylglycerols and free fatty acids was submitted to a filtration step to retain in the retentate most of the saturated fatty acids, with melting peaks ranging from ‐31.9 °C to +14.7 °C obtained by differential scanning calorimetry. This step allowed a significant increase of polyunsaturated fatty acids (PUFA) from 39.2 mol‐% in the crude oil to 43.3% in the permeate. The remaining free fatty acids in the permeate (20.2 wt‐%) was re‐esterified with an immobilized 1, 3‐specific lipase IM60. Acylglycerols synthesis reached 90% in optimized conditions. After 48 h of reaction, the distribution of monoacylglycerols, diacylglycerols and triacylglycerols was 22.1, 28.7, 43.4 (w/w), respectively. The re‐esterification step did not modify the PUFA content obtained after membrane filtration.     

Aqueous enzymatic oil extraction from Irvingia gabonensis seed kernels

The objective of this study was to extract the fat from Irvingia gabonensis kernels without using organic solvent but by using the enzyme aqueous oil extraction process. The aqueous dispersion of kernel flour of bush mango was treated with a protease (Alcalase®), a pectinase (Pectinex®) and a mixture of cell wall‐degrading enzymes (Viscozyme®) before centrifugation. The yield of oil extracted was calculated in comparison with the chemical extraction method using hexane as solvent. A central composite experimental design was used for the determination of optimized conditions. The results showed that aqueous extraction without enzyme allows recovering 27.4% of the kernel oil. When Alcalase, Pectinex and Viscozyme were added separately, the oil yields were 35.0, 42.2 and 68.0%, respectively. Optimized conditions for Viscozyme resulted in a model of oil yield with a high coefficient of determination (r² = 0.94). These conditions were the following: kernel‐to‐water ratio 0.11–0.19, concentration of enzyme 1.4–2.0%, and time of incubation 14–18 h. Confirmation of the model led to 83.0% oil yield after treatment of the kernel flour at a kernel‐to‐water ratio of 0.16, using 2% Viscozyme for 18 h. Under the same conditions, followed by addition of 1% Alcalase for 2 h, the yield was 90.0%.     

On‐line LC‐NMR‐MS characterization of sesame oil extracts and assessment of their antioxidant activity

Sesame lignans were isolated by solvent extraction and subsequently purified by solvent crystallization from crude, unroasted sesame oil, and a sesame oil deodorizer distillate. In addition, an aliquot of the purified sesame oil extract was treated with camphorsulfonic acid to obtain a sesaminol‐enriched extract. The sesame lignan composition of the extracts was characterized by on‐line liquid chromatography nuclear magnetic resonance spectroscopy mass spectrometry coupling (LC‐NMR‐MS). The effect of the sesame oil extracts as well as pure sesame lignans and γ‐tocopherol on the oxidative stability of sunflower oil (lignan‐free) was studied by the Rancimat assay. The Rancimat assay revealed the following oxidative stability order: sesame oil extract < sesame oil deodorizer distillate < sunflower oil (no added sesame oil extracts) < sesamol < sesaminol‐enriched sesame oil extract. In addition, the radical‐scavenging capacity of these extracts was assessed by the Trolox® equivalent antioxidant capacity (TEAC) assay. The TEAC assay revealed a slightly different AOX activity order: sesamin < sesame oil extract < sesaminol‐enriched sesame oil extract < sesamol. In conclusion, the sesaminol‐enriched extract revealed strong antioxidant activity and is therefore suitable to increase the oxidative stability of edible oils high in polyunsaturated fatty acids.     

Chemical Characterization of a High‐Oleic Soybean Oil

High‐oleic low‐linolenic acid soybean oil (HOLLSB, Plenish^®) is an emerging new oil with projections of rapid expansion in the USA. HOLLSB has important technological advantages, which are expected to drive a gradual replacement of commodity oils used in food applications such as soybean oil. A key technological advantage of HOLLSB is its relatively high oxidation stability. This oxidation stability is the result of a favorable fatty acid composition, high (76%) oleic acid, low linoleic (6.7%), and alpha‐linolenic (1.6%) acids, and high concentration of tocopherols (936 ppm) after refining, enriched with the gamma‐homolog (586 ppm). A detailed analysis of the fatty acid composition of this HOLLSB by gas chromatography–mass spectrometry allowed the identification and structural determination of 9‐cis‐heptadecenoic acid (or 17:1n‐8). To our knowledge, this is the first time 9‐cis‐heptadecenoic acid has been unequivocally reported in soybean oil. This unusual fatty acid component has the potential to be used as a single authenticity marker for the quantitative assessment of soybean oil. The Rancimat induction period (IP) of Plenish^® (16.1 hours) was higher than those of other commercially available high‐oleic oils, such as canola (13.4 hours), and Vistive^® Gold (10 hours), a different variety of soybean oil. Plenish^® showed the same IP as high‐oleic sunflower oil. Plenish^® shows a modest increase in oxidation stability with the external addition or relatively high concentrations of tocopherols. The characteristic high oxidative stability of Plenish^® may be further enhanced with the use of nontocopherol antioxidants.     

Flüssig/Flüssig‐Extraktion von Indium aus sauren Lösungen

The extraction of indium from a synthetic sulfate‐containing solution using commercial reagents (Cyanex 272, DEHPA, and Cyanex 923) is evaluated on a comparative basis. The extraction profiles of indium (III) were examined with regard to the reagent concentration, the pH value of the aqueous solution, and the indium concentration in a low phase ratio of 1:10. DEHPA and Cyanex 272 are, in contrast to Cyanex 923, very well suited for the extraction of indium. Re‐extraction with HCl and H₂SO₄ is compared.     

COMPOSITION OF CYANEX® 923, CYANEX® 925, CYANEX® 921 AND TOPO

ABSTRACT

The composition of commercial reagents CYANEX® 923, CYANEX® 925, CYANEX® 921 and TOPO was investigated by GC/MS. CYANEX® 923 contains 18 components. 17 compounds were identified as trialkylphosphine oxides, mainly with normal (92.4) hexyl and octyl groups. CYANEX® 925 consists of 19 components. The reagent contains 65.9% kyphosphine oxides, mainly with isooctyl groups. The reagent contains also trialkylphosphine sulphides, dialkyldithiophosphinic acids and dialkyldisulphides having octyl and butyl groups. Trialkylphosphine sulphides and dialkyldithiophosphinic acids are present in amount of 26.8% be also considered as the active substance. CYANEX® 921 and TOPO are high quality reagents with the content of the active substance of about 99%. Trioctylphosphine oxide is the main component.     

Investigation of liquid–liquid phase equilibria for reactive extraction of lactic acid with organophosphorus solvents

BACKGROUND: Lactic acid is a versatile commodity chemical with a variety of applications. Synthesis of lactic acid either through fermentation of carbohydrates or through chemical synthesis is state of the art. Separation from dilute aqueous solution is complex and accounts for the major part of production costs. Reactive extraction based on reversible adduct formation is a promising alternative for the separation of lactic acid. RESULTS: Extraction was carried out with the organophosphorus solvents tri‐n‐butyl phosphate, tri‐n‐octylphosphine oxide and Cyanex 923. Shellsol T was used as diluent. Partition coefficients increase with increasing extractant content and decreasing temperature. Cyanex 923 has several advantages compared with tri‐n‐butyl phosphate and tri‐n‐octylphosphine oxide with respect to lactic acid distribution and hydrodynamic properties. Liquid‐liquid phase equilibria for lactic acid extraction with Cyanex 923 were modeled. Selectivity of lactic acid extraction with respect to glycolic acid and formic acid was discussed. CONCLUSION: The organophosphorus extractant Cyanex 923 was found to be an appropriate solvent for lactic acid extraction from aqueous solutions. Experimental data and model data based on the Law of Mass Action showed good agreement. Lactic acid extraction from multi‐acid solution showed good selectivity compared with glycolic acid. Lactic acid selectivity is low with respect to formic acid. © 2012 Society of Chemical Industry     

Characterisation of Moringa stenopetala seed oil variety “Marigat” from island Kokwa

The oil from Moringa stenopetala seeds variety Marigat from the island Kokwa was extracted using 3 different procedures including cold press (CP), extraction with n‐hexane and extraction with a mixture of chloroform:methanol (1:1) (CM). The yield of oil was 35.7% (CP) to 44.9% (CM). The density, refractive index, colour, smoke point, viscosity, acidity, saponification value, iodine value, fatty acid methyl esters, sterols, tocopherols (by high‐performance liquid chromatography), peroxide value, Eequation/tex2gif-stack-1.gif at 232 nm and the susceptibility to oxidation measured by the Rancimat method were determined. The oil was found to contain high levels of unsaturated fatty acids, especially oleic (up to 76.40%). The dominant saturated acids were behenic (up to 6.01%) and palmitic (up to 6.21%). The oil was also found to contain high levels of β‐sitosterol (up to 52.19%%of total sterols), stigmasterol (up to 16.53% of total sterols) and campesterol (up to 14.26% of total sterols). α‐, β‐ and δ‐tocopherols were detected up to levels of 98.00, 44.50 and 82.41 mg/kg of oil, respectively. The reduction of the induction period (at 120 °C) of M. stenopetala seed oil ranged from 29.4% to 54.7% after degumming. The M. stenopetala seed oil showed high stability to oxidative rancidity. The results of all the above determinations were compared with those of a commercial virgin olive oil and Moringa oleifera seed oil.     

RECOVERY OF PHENOL WITH CYANEX® 923 IN MEMBRANE EXTRACTION-STRIPPING SYSTEMS

The recovery of phenol from aqueous solutions with CYANEX® 923 was studied. Classical dispersive extraction and three membrane extraction-stripping systems (bulk liquid membranes, three-phase hollow fiber contactor and two hollow fiber modules set-up) were used. It was found that CYANEX® 923 was a convenient carrier for recovery of phenol from aqueous streams in extraction-stripping membrane processes. The problem of emulsion formation, so important in dispersive extraction, was avoided. Both mass transfer experiments in different membrane systems and measurement of the dynamic interfacial tension demonstrated importance of the interfacial phenomena occurring in the stripping stage. A blocking of this interface was observed that resulted in a decrease of phenol mass transfer.     

Analysis of lipids extracted from salmon (Salmo salar) heads by commercial proteolytic enzymes

Fresh salmon heads were submitted to controlled proteolysis using food‐grade commercial enzymes (Alcalase®, Neutrase® and Protamex?). The release of oil under mild conditions (60°, 2 h) compared favourably with organic solvent extraction (19.8% vs. 21.5%). Lipids extracted by solvent and lipids resulting from enzymatic processes displayed a similar content of PUFA (about 35%), mainly eicosapentaenoic acid (EPA; 8.4% vs. 7.7%) and docosahexaenoic acid (DHA; 12.1% vs. 11.9%). Thin‐layer chromatography (TLC‐FID Iatroscan) showed that the polar lipid fraction accounted for 55% of total lipids (phosphatidylethanolamine, 20.7%; phosphatidylcholine, 14.8%). Salmon head phospholipids may be more effective carriers of highly unsaturated fatty acids to specific tissues than triacylglycerols, as shown by their content in EPA (10.3 and 6.9%, respectively) and DHA (33.1 and 9.1%, respectively).     

Effect of Oils Extracted from Plant Seeds on the Growth and Lipolytic Activity of <Emphasis Type="Italic">Yarrowia lipolytica</Emphasis> Yeast

This study was aimed at evaluating the capability of Yarrowia lipolytica W29 for the synthesis of lipolytic enzymes in a medium containing plant oils from non‐conventional sources with some components displaying bioactivity. Oils from almond, hazelnut, and coriander seeds were obtained by using n‐hexane (Soxhlet method) and a chloroform/methanol mixture of solvents (Folch method), and their effect on the growth and lipolytic activity of Y. lipolytica was compared. A comparison of these two extraction methods showed that the extraction with n‐hexane was less effective regarding the oil extraction yields than the extraction conducted according to Folch's procedure. The lipolytic activity of the studied yeast was higher in the culture media containing oils extracted with the Soxhlet method than the Folch method but it was lower compared to olive oil medium. Among all oils tested, almond oil extracted with n‐hexane was the best inducer of extracellular lipases synthesized by Y. lipolytica. Its lipolytic activity achieved the maximum value of 2.33 U/mL after 48 h of culture. After 24 h of culture, it was close to the value obtained for the medium containing olive oil. Almond oil was a source of oleic and linoleic acids, which may determine differences in the lipolytic activity. The linoleic acid content in almond oil was higher than that found in other oils. When n‐hexane was used for extraction, the resultant oils were characterized by lower contents of polyphenols and poorer antioxidative activity.     

Degumming rice bran oil using phospholipase‐A1

The efficacy of enzymatic degumming was assessed using the third generation phospholipase‐A₁, Lecitase®‐Ultra (EC 3.1.1.3) from Thermomyces lanuginosa/Fusarium oxysporum with different qualities of crude rice bran oil. The phosphorus content in the oil reduced to ～10 mg/kg from an initial level of 390 mg/kg after 2 h of incubation period at 50°C. However, in the solvent‐phase degumming, there was practically no phospholipid reduction at lower water content (2%) due to the poor contact between the highly nonpolar solvent and the aqueous phase (citric acid, NaOH, and enzyme solutions). Increasing the water content to 20% reduced the phosphorus level in the degummed‐oil to 71 mg/kg but did not match the performance of oil‐phase degumming. The degumming efficiency of Lecitase®‐Ultra was effective in oil‐phase and suitable for practical application. Solvent‐phase enzymatic degumming offers more benefits but needs greater efforts to overcome the challenges.     

Direct Derivatization vs Aqueous Extraction Methods of Fecal Free Fatty Acids for GC–MS Analysis

A comprehensive and accurate determination of free fatty acids (FFA) is required for fecal metabolomic investigations. The present study compares three aqueous extraction methods (1) ULTRA‐TURRAX^®, (2) whirl mixing and (3) basic ULTRA‐TURRAX extraction of fecal FFA with a direct derivatization approach using ethyl chloroformate as the derivatization reagent before determination by gas chromatography–mass spectrometry. The direct derivatization method resulted in significantly higher estimations (P < 0.01) of short‐ and long‐chain fatty acids than was the case when applying the aqueous extraction methods using ULTRA‐TURRAX, whirl mixing, or basic ULTRA‐TURRAX extraction before the derivatization step. Thus, avoiding an aqueous extraction before derivatization reduces the loss of volatile short‐chain FFA and the less water‐soluble long‐chain FFA.     

Liquid-Liquid Equilibrium Study of Phenol Extraction with Cyanex 923

Abstract

Although phenol extraction with Cyanex 923 has widely been studied, liquid-liquid equilibrium between phenol and undiluted Cyanex 923 has not been thoroughly investigated. Many factors influence the phenol extraction with undiluted Cyanex 923. Increasing the phenol concentration causes a water molecule replacement in the extractant by phenol molecules. Increasing the pH value above 12 decreases the phenol distribution coefficient K_D by 99.9%. A temperature increase from 15°C to 65°C results in a K_D decrease of 70%. With increasing salt content K_D increases due to salting-out. Adding organic acids stabilizes phenol in the aqueous phase and obstructs the extraction.     

Isopropyl Alcohol Extraction of De‐hulled Yellow Mustard Flour

Vegetable oils are typically extracted with hexane; however, health and environmental concerns over its use have prompted the search for alternative solvents. Mustard oil was extracted with isopropyl alcohol (IPA) to produce an IPA‐oil miscella suitable for industrial applications. Single‐stage extraction resulted in 87.6 % oil yield at a 10:1 (v/w) IPA/flour ratio. Multiple‐stage extraction resulted in higher extraction efficiency with lower IPA use. Four‐stage cross‐current extraction at an IPA/flour ratio of 2:1 (v/w) per stage resulted in 93.7 % oil yield. At 45 °C, a 91.5 % oil yield was achieved with three‐stage extraction using a 2:1 (v/w) IPA/flour ratio. Any changes to the pH of the mixture resulted in reduced oil yield. Water also reduced the extraction efficiency. The azeotropic IPA solution containing 13 % water extracted ~40 % less oil than did dry IPA in both single and multiple‐stage extractions. Some polar compounds were also extracted, including sugars; however, protein extraction was negligible. The protein left in the extracted meal was not degraded or lost during the extraction. The results suggest that IPA is an excellent solvent for mustard oil, but water content exceeding 5 % in the solvent adversely affects the oil extraction and reuse of the IPA.     

Enzymatic oil‐degumming by a novel microbial phospholipase

Phospholipase A‐mediated oil‐degumming is a well‐established process step (Enzy‐Max^®) in physical refining of vegetable oils (rape seed, soy bean, sunflower seed). A screening programme for microbial phospholipases of type A has been carried out. The target has been to develop a stable and robust phospholipase with optimal oil‐degumming performance in the pH‐range 4—5 and in the temperature range 30— 70 °C. One phospholipase of type A1 from Fusarium oxysporum, given the trade name Lecitase^® Novo, has been studied in detail. Some of the characteristics of this novel microbial phospholipase in the oil‐degumming application are: pH optimum ∼5, temperature optimum 40—45 °C. In laboratory tests the new phospholipase Lecitase^® Novo has proven to be superior to porcine pancreatic Lecitase^® 10L and other phospholipases with respect to oil‐degumming performance, and it has proven to be suited for degumming of different oil qualities ranging from water‐degummed to crude oil. A further advantage is that the new phospholipase acts at very low water content, which will make the problematic sludge recycling in the EnzyMax^® process superfluous. As demonstrated by an HPLC study, phospholipase‐mediated degumming is a unique process quite distinct from the well‐known acid degumming variations, since the phospholipids (both hydratable and non‐hydratable) present in the oil are hydrolysed to the corresponding lyso‐phospholipids, which migrate to the aqueous phase under the conditions employed. Lecitase^® Novo was introduced successfully for degumming of rapeseed oil at Cereol (Mannheim, Germany) mid 2000.