Separation of dilute aqueous butanol and acetone solutions by pervaporation through liquid membranes

A simultaneous extraction-stripping process is proposed for separating volatile products from fermentation broths, it is based on pervaporation through a liquid membrane supported with a hydrophobic porous membrane. The liquid membrane prepared with oleyl alcohol was selected as the most suitable for separating volatile products resulting from acetone-butanol fermentation. The separation performance and stability of the oleyl alcohol liquid membrane were investigated by using dilute aqueous butanol and acetone solutions. The oleyl alcohol liquid membrane was found to be superior by far in both selectivity and permeability of butanol to the better known silicone rubber membrane in its high selectivity for alcohols. Using the oleyl alcohol liquid membrane, the dilute aqueous butanol solutions of around 4 g/L obtained in acetone-butanol fermentation could be concentrated up to 100 times. The stability of this liquid membrane was also quite good as long as the surface tension of the feed solution was less than the critical surface tension of the support membrane. No change in the separation performance was found after the continuous usage in a long period of 100 h.     

Simultaneous extraction and concentration of penicillin G by hollow fiber renewal liquid membrane

In this article, hollow fiber renewal liquid membrane (HFRLM) technique was used for recovery of penicillin G from aqueous solution. The organic solution of 7 vol % di‐n‐octylamine (DOA) + 30 vol % iso‐octanol + kerosene was used as liquid membrane phase, and Na₂CO₃ aqueous solution was used as stripping phase. Experiments were performed as a function of carrier concentration in the organic phase, organic/aqueous volume ratio, pH, and initial penicillin G concentration in the feed phase, pH in the stripping phase, flow rates, etc. The results showed that the HFRLM process was stable and could carry out simultaneous extraction and concentration of penicillin G from aqueous solutions. As a carrier facilitated transport process, the addition of DOA in organic phase could greatly enhance the mass transfer rate; and there was a favorable organic/aqueous volume ratio of 1:20 to 1:30 for this system. The mass transfer flux and overall mass transfer coefficient increased with decreasing pH in the feed phase and increasing pH in the stripping phase, because of variation of the mass transfer driving force caused by pH gradient and distribution equilibrium. The flow rate of the shell side had significant influence on the mass transfer performance, whereas the effect of flow rate of lumen side on the mass transfer performance was slight because of the mass transfer intensification of renewal effect in the lumen side. The results indicated that the HFRLM process was a promising method for the recovery of penicillin G from aqueous solutions. © 2009 American Institute of Chemical Engineers Biotechnol. Prog., 2009     

Extraction of tylosin from its aqueous solutions by Rotating Film-pertraction

Removal of tylosin from its dilute aqueous solutions was studied applying the Rotating Film-pertraction technique. Non-toxic and practically water insoluble alcohols as n-octanol and n-decanol were used as intermediate, membrane liquid. A 0.001 mol/l solution of HCl was used as a stripping phase. Effects of temperature, feed phase pH-value and solute concentration on antibiotic distribution coefficients were obtained for both systems. It was found that the first two parameters have important effect, while the solute concentration in the studied range (0.02-0.1 g/l) did not modify these coefficients. Results obtained show that the first pertraction step - solute extraction from the feed - is a very fast process, while the second one - the alcohol stripping - is relatively slow, in particular when octanol was used as membrane phase. A mathematical model was proposed and used for evaluation of corresponding local mass transfer coefficients.     

Emulsion liquid membrane extraction of lactic acid from aqueous solutions and fermentation broth

Studies on the batch extraction of lactic acid using an emulsion liquid membrane system are reported. The membrane phase consists of the tertiary amine carrier Alamine 336 and the surfactant Span 80 dissolved in n-heptane/paraffin and aqueous solutions of sodium carbonate in the internal phase. The effects of internal phase reagent, extraction temperature, and initial external phase pH on the extraction efficiency and the emulsion swelling are examined. A statistical factorial experiment on extraction from clarified lactic acid fermentation broth was carried out to obtain knowledge of the performance of the extraction system from a broth. The extraction efficiency from the fermentation broth is found to be lower as compared to aqueous solutions of pure lactic acid. The effect of pH and the presence of other ionic species on selectivity are discussed. (c) 1993 John Wiley & Sons, Inc.     

Separation of L-valine from fermentation broths using a supported liquid membrane

A carrier-mediated counter transport process is proposed to separate and to purify an amino acid produced by microbial fermentation. The case of L-valine permeation through a liquid membrane, constituted by a solution of Aliquat 336 in decanol and supported by a hydrophobic microporous membrane, is reported. A mathematical model was developed to estimate distribution coefficients and permeabilities and to predict the influence of hydrodynamic and pH conditions on supported liquid membrane (SLM) performances. Optimum conditions for the transport and the concentration of valine were achieved with synthetic aqueous valine solutions. Series of experiments on fermentation broths, where molasses and biomass contents were varied, permitted pointing out the role of the broth composition on the kinetics and yields of separation. The selectivity of transport of valine by an Aliquat 336/decanol liquid membrane was about 10 toward molasses dyes, 100 toward glucose, and beyond 1000 toward sucrose. This allowed us to achieve the recovery and one step of purification of the product in a single operation. The stability of the Aliquat 336/decanol liquid membrane was sufficient to ensure a selective transport of valine during a continuous run lasting 18 days.     

Metal biosorption-flotation. Application to cadmium removal

Biosorption, using suspended non-living biomass, and flotation (for consequent solid/liquid separation of the metal-loaded biomass) have been studied in the laboratory as a possible combined process, for the removal of toxic metals (i.e. cadmium) from dilute aqueous solutions. The various parameters of the process were investigated in depth, including re-use of biosorbent. A filter aid (contained in the biomass industrial waste used) was found not really to interfere. -potential measurements of the aforementioned system were also carried out. Promising results were obtained during continuous-flow experiments. A flotation residence time of 4 min was achieved. Metal removal and suspended biomass recovery were generally over 95%.     

Recovery of dilute acetone–butanol–ethanol (ABE) solvents from aqueous solutions via membrane distillation

The simultaneous recovery of dilute acetone-butanol-ethanol (ABE) solvents from aqueous solutions by air gap membrane distillation was theoretically assessed. A previously developed and validated Stefan-Maxwell based mathematical model was used for this purpose. It was found that membrane distillation could successfully be used for the recovery of these solvents. Interestingly it was found that butanol could be separated with the highest selectivity and flux though it has the highest boiling point. The effect of operating conditions such as feed and cooling surface temperatures, air gap width, and individual component concentration on the flux and selectivity of these solvents was examined and discussed in this paper.     

Facilitated transport of lactic acid in a stirred transfer cell

The application of liquid membrane extraction to the recovery of lactic acid from model systems and fermentation media was investigated. An experimental study of the facilitated transport of lactic acid using ALIQUAT 336 as a mobile carrier in a stirred transfer cell is reported. The effect of stirring speed, initial lactic acid concentration, carrier concentration, and NaCl as a reagent in the acceptor phase are considered. (c) 1994 John Wiley & Sons, Inc.     

Predispersed solvent extraction of succinic acid aqueous solution by colloidal liquid aphrons in column

A study of the PDSE (predispersed solvent extraction) for succinic acid by colloidal liquid aphrons was conducted. The organic phase contaning TOA (tri-n-octylamine) and 1-octanol permits a selective extraction of succinic acid from its aqueous solution. There was no difference of the extractability of PDSE and that of conventional mixer-settler type extraction. Taking into account the no mechanical mixing in PDSE, it was concluded that the PDSE process is more adaptive than the conventional mixer-settler type extraction process. From mass transfer analysis at the various concentration of TOA in counter-current continuous operation, the concentration of TOA had no influence on the mass transfer coefficient. The loading values in continuous PDSE were almost same as those in batch operation.     

Selective recovery of uranium and thorium ions from dilute aqueous solutions by animal biopolymers

Selective actinide ion recovery from dilute, aqueous, multication waste streams is an important problem. The recovery of uranium (U) and thorium (Th) by various animal biopolymers was examined. Of four species of biopolymers tested, a high uptake of uranium and thorium was found in hen eggshell membrane (ESM) and silk proteins, with the maximum uranium and thorium recovery exceeding 98% and 79%, respectively. The uptake of U and Th was significantly affected by the pH of the solution. The optimum pH values were 6 and 3 for the uptake of U and Th, respectively. The effect of temperature differed with the metal. The uptake of U decreased with increasing temperature (30–50°C), whereas the Th uptake increased with increasing temperature. Selective recovery of U and Th from dilute aqueous binary and multimetal solutions was also examined. ESM and silk proteins tested were effective and selective for removing each metal by controlling the pH and temperature of the solution. In multimetal systems, the order of sorption of ESM proteins was preferential: U > Cu > Cd > Mn > Pb > Th > Ni > Co > Zn at pH 6 and Th > U > Cu > Pb > Cd > Mn > Co > Ni = Zn at pH 3. These biopolymers appear to have potential for use in a commercial process for actinide recovery from actinide-containing wastewater.     

Chiral calix[4]arenes bearing amino alcohol functionality as membrane carriers for transport of chiral amino acid methylesters and mandelic acid

Novel chiral calix[4]arene derivatives bearing amino alcohol moieties at the lower rim have been synthesized from the reaction of p-tert-butylcalix[4]arene diester with various amino alcohols. The transport of amino acid esters (phenylglycine, phenylalanine, and tryptophan methyl esters hydrochloride) and mandelic acid were studied through chloroform bulk liquid membrane system using chiral calix[4]arenes 15-20. All these receptors have been found to act as carriers for transport of aromatic amino acid methylesters and mandelic acid from the aqueous source phase to the aqueous receiving phase. The influence of calixarene and guest structures upon transport through liquid membrane is discussed.     

STUDIES ON THE PERMEABILITY OF MEMBRANES : II. DETERMINATION OF IONIC TRANSFER NUMBERS IN MEMBRANES FROM CONCENTRATION CHAINS.

The ionic transfer number in an electrolyte solution in the pores of a narrow pored collodion membrane depends much more on the concentration than it does in a free aqueous solution. The potential difference of two solutions of the same electrolyte in different concentration depends largely on the concentration range. The ratio of the concentrations on the two sides was always 1:2 in the experiments; the concentration range was varied. It is shown that the transfer number of Cl, calculated from the P.D. measured, is very small in dilute solution (down to .02 and less in some cases), whereas it approaches the value .5 holding for free aqueous solutions when the concentration range is raised. The differences for the transfer number of Cl, according to the cation (H, K, Na, Li), can be recognized and show the same order as in free aqueous solution. But even in LiCl, where in an ordinary aqueous solution the transfer number of Cl is always > .5, this number is very low in the case of the membrane (e.g. < .05 in .01 M solution).     

A hybrid process for chiral separation of compound‐forming systems

The resolution of chiral compound‐forming systems using hybrid processes was discussed recently. The concept is of large relevance as these systems form the majority of chiral substances. In this study, a novel hybrid process is presented, which combines pertraction and subsequent preferential crystallization and is applicable for the resolution of such systems. A supported liquid membrane applied in a pertraction process provides enantiomeric enrichment. This membrane contains a solution of a chiral compound acting as a selective carrier for one of the enantiomers. Screening of a large number of liquid membranes and potential carriers using the conductor‐like screening model for realistic solvation method led to the identification of several promising carriers, which were tested experimentally in several pertraction runs aiming to yield enriched (+)‐(S)‐mandelic acid (MA) solutions from racemic feed solutions. The most promising system consisted of tetrahydronaphthalene as liquid membrane and hydroquinine‐4‐methyl‐2‐quinolylether (HMQ) as chiral carrier achieving enantiomeric excesses of 15% in average. The successful production of (+)‐(S)‐MA with a purity above 96% from enriched solutions by subsequent preferential crystallization proved the applicability of the hybrid process. Chirality, 2011. © 2010 Wiley‐Liss, Inc.     

Effect of salts on the extraction characteristics of succinic acid by predispersed solvent extraction

Predispersed solvent extraction (PDSE) of succinic acid with Tri-n-octylamine (TOA) dissolved in 1-octanol from aqueous solutions of 50 g/L succinic acid was examined. It was found that the equilibrium data in PDSE was equal to that in conventional solvent extraction in spite of the lack of mechanical mixing in PDSE. The influence of salts on succinic acid extraction and the stability of colloidal liquid aphrons (CLAs) were also investigated. Results indicated that in the presence of sodium chloride, less succinic acid was extracted by CLAs and the stability of CLAs decreased. However, the stability of CLAs was sufficient to make PDSE practically applicable to real fermentation broth, considering the concentration range of salts in the fermentation process for succinic acid.     

Extraction of laminarin from Saccharina latissima seaweed using cross-flow filtration

Laminarin is a low-molecular-weight polysaccharide found in seaweed (kelp), often in equal concentrations to that in the commercially important hydrocolloid alginate. However, while alginate can be easily recovered by dissolution followed by acid precipitation, for laminarin, there is no such straightforward way of recovering it. Laminarin can be used as dietary fiber and, if efficiently extracted, it may be used for functional food/feed applications and as a component in plant defense stimulants for agriculture. One way of concentrating laminarin from dilute solutions is to press the solution through ultrafine membranes that the molecules cannot pass through. When alginate is extracted, an acid pretreatment step is used and the dilute acid residue from that process also contains laminarin. We used cross-flow filtration to concentrate laminarin from Saccharina latissima, retrieving it from the dilute acid solution of the acid pretreatment of an alginate extraction. Three ceramic membranes with 5, 15, and 50 kDa molecular weight cutoffs were used, and the pressure, temperature, and feed velocity were altered to reveal which parameters controlled the flow through the membrane and how efficiently laminarin was concentrated. The effects on laminarin extraction for fresh vs. frozen biomass were evaluated showing that frozen biomass releases more laminarin with a similar biomass homogenization technique. Thermal and microbial degradation of the feed components was studied during the course of the filtrations, showing that microbial degradation can affect the laminarin concentration, while the temperature of the process ~ 65 °C had little impact on laminarin. The techniques used to monitor the components in the feed and permeate during filtration were nuclear magnetic resonance, ¹H-NMR, and size exclusion chromatography. The filtrations were performed in a pilot-size filtration unit with ceramic membranes (ZrO₂/TiO₂, TiO₂-Al₂O support, 0.08 m²). To be able to operate without quick membrane fouling, the most important parameter was to have a high liquid velocity over the membrane, 4.7 m?s^?1. A good technique to concentrate laminarin was to prefilter it through a 50-kDa membrane using 2 bar liquid pressure and to concentrate it over a 5-kDa membrane using 5-bar liquid pressure. With these settings, the liquid flux through the filter became 60–80 and 30–40 L?m^?2?h^?1 over the 50-kDa and 5-kDa membrane.

     

Lysine peptides induce lipid intermixing but not fusion between phosphatidic acid-containing vesicles

Penta(L-lysine) and poly(L-lysine) (but not di- or tri(-L-lysine)) were found to induce rapid and extensive phospholipid intermixing between unilamellar vesicles consisting largely of phosphatidic acid and phosphatidylethanolamine, without causing significant intermixing of, nor leakage from, the encapsulated aqueous spaces. Neither did the size of such vesicles increase after treatment with lysine peptide, as determined by gel chromatography. The results suggest that lysine oligo-(or poly-) peptides may induce reversible semifusion between vesicles, but not complete membrane fusion.

Pentalysine Polylysine Phosphatidic acid Lipid intermixing Membrane fusion     

Liquid membrane extraction of bio-active amphiphilic substances: Recovery of surfactin

The interest of application of liquid membrane (pertraction) processes for recovery of biosurfactants from aqueous media was demonstrated. Transport of pure surfactin in three-liquid-phase system was studied. Surfactin was successfully extracted from slightly acid media (pH 5.65–6.05) applying batch pertraction in a rotating discs contactor and using n-heptane as liquid membrane. The process efficiency was found to be strongly affected by the feed solution acidity (83% at pH_F 6.05 and 97% at pH_F 5.65 after 4 h pertraction).An atypical pH effect was observed when the behaviour of surfactin extraction from aqueous media by non-polar solvents (n-heptane and n-octane) was studied. The obtained high extraction degrees from both acid and basic media and the clearly reduced degree of extraction from neutral media could be attributed to the different conformations of surfactin in these media.     

乳化液膜提取浓缩柠檬酸的研究

本文研究了采用W／O型乳化液膜提取柠檬酸过程中影响柠檬酸传质的主要因素。讨论了载体、助溶剂、内相反革试剂等对柠檬酸萃取的影响．实验结果表明：柠檬酸的提取率随载体三烷基胺（C7～10）和内相反萃试剂Na₂CO₃浓度的增加而增加．膜相中加入正辛醇能显著提高柠檬酸的传质速率。     

Biosynthesis of epsilon-poly-L-lysine in a cell-free system of Streptomyces albulus

epsilon-Poly-L-lysine (epsilon-PL) is a homo-poly-amino acid characterized by a peptide bond between carboxyl and epsilon-amino groups of L-lysine. Here we report the cell-free synthesis of epsilon-PL by a sensitive radioisotopic epsilon-PL assay system. In vitro epsilon-PL synthesis depended on ATP and was not affected by ribonuclease, kanamycin, or chloramphenicol. epsilon-PL synthesizing activity was detected in the membrane fraction. The reaction product, epsilon-PL, from L-lysine was identified by MALDI-TOF MS and the number of lysine residues of the epsilon-PL products was apparently 11-34. These results suggest that the biosynthesis of epsilon-PL is nonribosomal peptide synthesis and is catalyzed by membrane bound enzyme(s). The enzyme preparation showing the epsilon-PL synthesizing activity also catalyzed lysine-dependent AMP production and an ATP-PPi exchange reaction, suggesting that L-lysine is adenylated in the first step of epsilon-PL biosynthesis.     

Extra-weak chemiluminescence of drugs. VIII. Extra-weak chemiluminescence arising from the amino-carbonyl reaction

Extra-weak chemiluminescence (CL) from amino-carbonyl reactions of L-lysine with various sugars and aldehydes in aqueous solution was examined. Amongst the aldehydes and sugars tested, glycolaldehyde and D -arabinose produced the highest CL intensity. The CL of the amino-carbonyl reaction reached a maximum after about 60 minutes. The CL was pH dependent, and a linear relation between CL intensity and hydroge-ion concentration was demonstrated. Low oxygen levels inhibited CL and no CL was produced in nitrogen purged solutions. Addition of cupric or ferrous ion, decreased the CL. The involvement of free radical intermediates was demonstrated by ESR. Our findings suggest that the CL of the amino-carbonyl reaction arises from free radicals derived from melanoidines or their intermediates. CL should prove useful for evaluating the stability of crude drugs extracted from natural resources that contain various amino acid derivatives protein and sugar components.