Membrane extraction for removal of acetic acid from biomass hydrolysates

Production of bioethanol from lignocellulosic biomass requires pretreatment of the biomass in order to improve the susceptibility of the cellulose to enzymatic hydrolysis to glucose. When dilute acid is used to perform this process, the hemicellulose is also hydrolyzed to its component sugars while simultaneously releasing acetyl groups attached to the hemicellulose backbone. Other compounds from the lignin and sugar degradation products are also produced that inhibit subsequent bioconversion of the solubilized sugars to the desired products. In this work we focused on removal of acetic acid from a dilute sulphuric acid pretreated corn stover hydrolysate.Acetic acid has been extracted into an organic phase at pH values below its pK_a. The organic phase diluent consisted of octanol. Alamine 336, a tertiary amine and Aliquat 336 a quaternary amine were used as the aliphatic amine extractants. Our results indicate more than 60% removal of acetic acid using Alamine 336. Extraction rates were much slower for Aliquat 336 probably due to the higher viscosity of the Aliquat 336/octanol phase.The presence of sulphate anions, as a result of dilute sulphuric acid pretreatment, results in the co-extraction of bisulphate anion. Bisulphate anion is preferentially extracted at pH values below its pK_a. Consequently the pH of the hydrolysate increases from between 1 and 2 to above 4.0 during extraction. In addition, extraction of low molecular weight lignins and phenolics is also observed. Thus the membrane extraction process developed here may be used not only for removal of acetic acid but also to adjust the pH of the hydrolysate to values that are more compatible for fermentation and to remove other inhibitory compounds.     

A hollow-fiber membrane extraction process for recovery and separation of lactic acid from aqueous solution

An energy-efficient hollow-fiber membrane extraction process was successfully developed to separate and recover lactic acid produced in fermentation. Although many fermentation processes have been developed for lactic acid production, and economical method for lactic acid recovery from the fermentation broth is still needed. Continuous extraction of lactic acid from a simulated aqueous stream was achieved by using Alamine 336 in 2-octanol contained in a hollow-fiber membrane extractor. In this process, the extractant was simultaneously regenerated by stripping with NaOH in a second membrane extractor, and the final product is a concentrated lactate salt solution. The extraction rate increased linearly with an increase in the Alamine 336 content in the solvent (from 5 to 40%). Increasing the concentration of the undissociated lactic acid in the feed solution by either increasing the lactate concentration (from 5 to 40 g/L) or decreasing the solution pH (from 5.0 to 4.0) also increased the extraction rate. Based on these observations, a reactive extraction model with a first-order reaction mechanism for both lactic acid and amine concentrations was proposed. The extraction rate also increased with an increase in the feed flow rate, but not the flow rates of solvent and the stripping solution, suggesting that the process was not limited by diffusion in the liquid films or membrane pores. A mathematical model considering both diffusion and chemical reaction in the extractor and back extractor was developed to simulate the process. The model fits the experimental data well and can be used in scale up design of the process.     

Studies on transport mechanism of Cr(VI) extraction from an acidic solution using liquid surfactant membranes

A mathematical model for analysing the extraction of Cr(VI) from aqueous acidic solution by emulsion liquid membrane using Aliquat 336 as extractant and NaOH as stripping agent has been presented. The existing models developed so far do not account for the existence of different forms of Cr(VI) ions in the aqueous phase depending on pH conditions. Accordingly, in the present model, reaction equilibrium has been considered instead of distribution coefficient to represent realistically the transport mechanism for this type of system through liquid surfactant membrane. Unlike other models, liquid–liquid equilibrium of sodium hydroxide-chloride of Aliquat 336 has also been considered. The carrier thus exists in the membrane phase in hydroxide and chloride forms and extraction of hexavalent chromium from the external phase proceeds by the two carriers. The validity of the model has been checked from comparison of the simulated curves and experimental data using chemical reaction equilibrium constant and D_eff/R² as fitting parameters.     

Membrane-mediated extractive fermentation for lactic acid production from cellulosic biomass

Lactic acid production from cellulosic biomass by cellulase andLactobacillus delbrueckii was studied in a fermenter-extractor employing a microporous hollow fiber membrane (MHF). This bioreactor system was operated under a fed-batch mode with continuous removal of lactic acid by anin situ extraction. A tertiary amine (Alamine 336) was used as an extractant for lactic acid. The extraction capacity of Alamine 336 is greatly enhanced by addition of alcohol. Long-chain alcohols serve well for this purpose since they are less toxic to micro-organism. Addition of kerosene, a diluent, was necessary to reduce the solvent viscosity. A solvent mixture of 20% Alamine 336, 40% oleyl alcohol, and 40% kerosene was found to be most effective in the extraction of lactic acid. Progressive change of pH from an initial value of 5.0 down to 4.3 has significantly improved the overall performance of the simultaneous saccharification and extractive fermentation over that of constant pH operation. The change of pH was applied to promote cell growth in the early phase, and extraction in the latter phase.     

Mathematical modeling for facilitated transport of Ge(IV) through supported liquid membrane containing Alamine 336

A mathematical model was developed for the germanium-facilitated transport from a medium containing tartaric acid using Alamine 336 as a carrier. Modeling was carried out based on the extraction constant (K _ext) obtained from the liquid–liquid extraction (LLX) modeling. The LLX data were achieved from experiments with conditions being Alamine 336 concentrations of 0.1–10% v/v from a solution containing about 1.378 mmol/L Ge (100 mg/L) and tartaric acid as an anionic complexant. The LLX model was attained using the equilibrium-based procedure and fitted to extraction experimental data for various carrier concentrations. This model presented an accurate extraction constant (K _ext = 0.02) used in the facilitated transport modeling. The flat sheet supported liquid membrane (FSSLM) experiments were conducted in the condition of 1.378 mmol/L Ge (100 mg/L), tartaric acid concentration of 2.760 mmol/L, 1 M HCl as a stripping phase and various Alamine 336 concentrations in the range of 0–35% v/v. The FSSLM model was developed according to the Fick’s law, the diffusional transport, and equilibrium equations. According to the model, mass transfer and diffusion coefficients for various concentrations of the carrier were found. In addition, the calculated and experimental values had a good correlation with together showing the validity of the model. This model can be used in the further process simulation such as hollow fiber SLMs.     

Solvent extraction of uranium(VI) and separation of vanadium(V) from sulfate solutions using Alamine 336

The present scientific study on uranium(VI) solvent extraction and vanadium(V) separation from sulfate solutions using Alamine 336 as an extractant diluted in kerosene was established. The preliminary experiments indicating the uranium extraction process will follow the solvation as well as ion-exchange mechanisms. In the present acid region (0.1–1.0 mol dm⁻³ H₂SO₄) it showing the ion-exchange type mechanism. Time (1–120 min) and temperature (25–55 °C) not influencing the present extraction system. Other experimental parameters like loading capacity of Alamine 336, stripping of uranium from loaded organic phase, recycling of Alamine 336 and separation of uranium(VI)/vanadium(V) was studied.     

Synthesis and primary biological evaluation of 188ReN-NEMPTDD

The recovery of uranium(VI) from chloride solution using a liquid emulsion membrane (LEM) technique was studied. The emulsion is constituted by the quaternary salt of benzyloctadecyldimethyl ammonium chloride (BODMAC, R₄NCl) as a carrier, kerosene as organic diluent, Span 80 as emulsifying agent and 0.5 mol/l Na₂CO₃ as stripping phase. The important variables affecting the LEM permeation process such as the concentrations of extractant, internal strip phase, types of organic diluent, and the presence of magnesium chloride or magnesium sulfate were investigated. It was found that, at a given condition, the maximum extraction rate of uranium(VI) reached 80%. The emulsion was stable at low pH in the presence of certain amounts of electrolytes such as NaCl and MgCl₂.     

Re(VII) extraction and separation from Mo(VI) by levextrel resins containing trialkyl amine

A synthetic method of novel trialkyl amine (N235, R₃N, R = C₈–C₁₀) Levextrel resin was described in this paper. The extraction behavior of rhenium(VII) and molybdenum(VI) with this N235 Levextrel resin has been studied. The mechanism of extraction of Re(VII) with the N235 Levextrel resin has been discussed briefly through equi-molar series method and the conventional slope analysis method. The optimal conditions of extraction and separation Mo(VI) and Re(VII) with the N235 Levextrel resin were determined. Also, its excellent extraction characteristics for Re(VII) were confirmed by extraction and stripping tests in a analog liquid solution containing Mo(VI) and Re(VII).     

Liquid-liquid extraction of Mo(VI) and V(V) by Primene JMT

The extraction equilibrium of pentavalent vanadium and hexavalent molybdenum with a benzene solution of primary amine Primene JMT sulphate has been investigated. The comparison of the extraction of aqueous solutions containing the salts of the elements and the solutions containing the mixture of Mo(VI) and V(V) was carried out. The attention was directed to the pH 2–6 region in which the heptamolybdates and decavanadates in prevail aqueous phase and to the region ≈1M H₂SO₄ which was suitable for the extraction separation of Mo(VI). The mechanism of extraction is discussed.     

Extraction,Spectrophotometric and Atomic Absorption Spectrophotometric Determination of Molybdenum with Caffeic Acid and Application in High Purity Grade Steel and Environmental Samples

Abstract

A new selective and sensitive method for extraction of yellow Mo (VI)-caffeic acid complex with a liquid ion exchanger, Aliquat 336 from 4.0 pH, and spectrophotometric determination of molybdenum in trace amounts is described. the molar absorptivity of the complex is 1.1 × 10⁵ 1 mol^?1 cm^?1 at 340 nm and the colour system obeys Beer's law in the range 0.04–0.99 ppm of Mo(VI). the molybdenum is also determined with AAS and the method is applied for its determination in steel and environmental samples.     

Liquid-supported membranes in chromium(VI) optical sensing: transport modelling

Flat sheet liquid-supported membranes (FSLSM) containing Aliquat 336 as a carrier have been evaluated as sample interface in an optical sensor for Cr(VI) monitoring. A model describing the transport mechanism of Cr(VI) through the membrane is reported. The model considers a diffusion process through a feed aqueous diffusion layer, a fast interfacial chemical reaction and a diffusion of ALQHCrO₄ and (ALQ)₂CrO₄ species through the membrane (Aliquat 336, ALQ). The mathematical equations describing the transport rate are derived and they correlate the membrane permeability coefficient to diffusional and equilibrium parameters as well as to the chemical composition of the system, i.e. extractant concentration in the membrane phase and acidity in the feed phase. The experimental data are explained by the derived equations and the diffusion resistances to mass transfer are evaluated. The influence of other experimental parameters, such as stirring speed in the feed phase and nature of the diluent and stripping agent on the transport is also discussed. Experiments with optical detection demonstrate the suitability of liquid-supported membranes (LSM) containing ALQ as interfaces for optical sensing.     

Solvent extraction of uranium(VI) and molybdenium(VI) by Alamine 310 and its mixtures from aqueous H3PO4 solution

Liquid-liquid extraction of uranium (VI) from aqueous phosphoric acid solution by triisodecylamine (Alamine 310), tri-n-butyl phosphate (TBP), di-n-pentyl sulfoxide (DPSO) and their mixtures in benzene in the range 1–10M aqueous H₃PO₄ shows that extraction is maximum (80%) in the higher acidity range 6–8 M. Extraction of this metal ion by bis(2,4,4-trimethylpentyl)phosphinicacid (Cyanex 301) and its mixtures studied in the range 0.2–1.0M aqueous H₃PO₄ is far from being quantitative. Antagonism in extraction by mixtures of extractants is observed in most of the cases. Extraction of molybdenum(VI) under identical conditions shows that it is quantitative in the lower acidity range upto 2M H₃PO₄. Separation of uranium(VI) from molybdenum(VI) is feasible by Alamine 310, TBP and DPSO, the order of efficiency being TBP>DPSO>Alamine 310.     

Kinetic study of uranium transport via a bulk liquid membrane containing Alamine 336 as a carrier

Journal of Radioanalytical and Nuclear Chemistry - A kinetic study of the uranium transport from the sulfate medium through the bulk liquid membrane was conducted by Alamine 336 as a carrier. The...     

A study on separation and extraction of four main alkaloids in Macleaya cordata (Willd) R. Br. with strip dispersion hybrid liquid membrane

A technique based on strip dispersion hybrid liquid membrane was developed for the separation and extraction of four main alkaloids from fruits of Macleaya cordata (Willd) R. Br. A microporous polypropylene membrane impregnated with an organic membrane solution comprised the heart of the strip dispersion hybrid liquid membrane system. The membrane solution was made by dissolving a cationic carrier, di‐(2‐ethylhexyl) phosphoric acid in an inexpensive, less toxic membrane solvent, kerosene. The transport of alkaloids from an aqueous feed solution through the membrane to a strip dispersion phase was driven by the concentration gradient of H⁺ and facilitated by di‐(2‐ethylhexyl) phosphoric acid. The effects of the extraction time and reuse times of the membrane, the strip solution composition, the carrier concentration, the volume ratio of the aqueous strip solution to the organic membrane solution, and the flow rates of the feed solution and the strip dispersion phase on the transport of alkaloids were investigated. Under the optimal conditions, the permeability coefficients obtained for the four main alkaloids allocryptopine, protopine, sanguinarine, and chelerythrine were 1.66, 1.99, 2.98, and 3.06×10^?4 cm/s, and the transport efficiencies were as high as 68, 77, 83, and 85%, respectively.     

Separation of Zr from Hf in acidic chloride solutions by using TOPO and its mixture with other extractants

Liquid–liquid extraction of Zr and Hf from chloride solutions was performed by using TOPO extractant in kerosene. An effective extraction of Zr from Hf was achieved selectively at 2.5–3 M HCl condition. Moreover, a mixture of TOPO with DOS, D2EHPA, Aliquat 336, Alamine 336 and Alamine 308 were tested in order to investigate the extraction behavior of Zr and Hf. The mixture of TOPO and D2EHPA was found to increase the extraction of Zr and Hf. In the extraction by the mixture of TOPO and amine, the extraction percentage of Zr and Hf was decreased with the increase of amine concentration due to the preferential extraction of HCl. Finally, among the mixtures of TOPO and other extractants tested in this study, the TOPO alone system was found to be better for the mutual separation of Zr and Hf in hydrochloric acid media.     

Cr(VI) ion removal from artificial waste water using supported liquid membrane

In this study, a novel flat-type synergic-supported liquid membrane was evaluated with a mixture of N-methyl-N,N,N-trioctylammonium chloride (Aliquat 336) and tributyl phosphate (TBP) as the carrier and kerosene as the diluent to remove Cr(VI) from synthetic waste water. The main parameters involved in the process were identified and optimised. The parameters were divided into two groups, those that were independent and those having an interaction. The parameters of the carrier/kerosene volumetric proportion and stirring rate were optimised individually due to their nature. The optimal values of these parameters were 0.5 and 500 min^?1, respectively, for a constant carrier/kerosene ratio and stirring rate in the designed experiments using the response surface method (RSM). The four parameters of TBP/Aliquat 336, chromium concentration in the feed phase, feed and product pH were optimised using RSM; it was observed that the TBP/Aliquat 336 ratio, feed pH, pH of the stripping phase and interaction of this parameter with feed concentration have the most important effects on the removal of Cr(VI). The optimal levels of these parameters were 0.61, 71.75 mg L^?1, 3.5 and 12.66 for the ratio of TBP/Aliquat 336, feed chromium concentration, pH of the feed and pH of the product, respectively. An experimental removal rate of 94.63 % at the optimized levels was obtained.     

Transport of U(VI) from sulphuric acid medium across supported liquid membrane (SLM) containing di-(2-ethylhexyl) phosphoric acid (D2EHPA)/n-dodecane as a carrier

This paper reports on the supported liquid membrane (SLM) based transport studies of U(VI) from sulphate medium using di-(2-ethylhexyl) phosphoric acid/n-dodecane as carrier. Polytetrafluoroethylene membrane was used as solid support and H₂SO₄ as receiver phase. The effects of various parameters such as receiver phase concentration, feed acidity, carrier concentration, U(VI) concentration, membrane thickness and membrane pore size on U(VI) transport had been investigated. With increase in H₂SO₄ concentrations and pH of feed solution there is an increase in U(VI) transport across the SLM. Similarly with increase in membrane thickness the U(VI) transport decrease whereas in case of pore size variation reverse results are obtained. The membrane thickness variation results showed that the U(VI) transport across the SLM is entirely diffusion controlled and the diffusion coefficient the D _(o) was calculated as 1.36 × 10^?7 cm² s^?1. Based on optimized condition, a scheme had been tested for selective recovery of U(VI) from ore leach solution containing a large number of other metal ions.     

Spectrophotometric determination of p.p.b. levels of long-chain amines in waters and raffinates

An analytical procedure is described for the determination of p.p.b. levels of long-chain amines in river and sea water and uranium processing raffinates. The method involves extraction of the amine as an ion-association complex with chromate from sulphuric acid media into chloroform. The extracted chromium(VI) is then determined spectrophotometrically with diphenylcarbazide. With a 100-ml sample, the limit of detection for Alamine 336 (a commercial tertiary amine mixture) is 15 p.p.b.     

Hybrid liquid membrane (HLM) system in separation technologies

A novel liquid membrane system, denoted hybrid liquid membrane (HLM), was developed for the separation of solutes (metal ions, acids, etc.). It utilizes a solution of an extracting reagent (carrier solution), flowing between membranes. The membranes, which separate the carrier solution from feed and receiving (strip) solutions, enable the transport of solutes, but block the transfer of the carrier to the feed or to the strip. Blocking the carrier is achieved through membranes hydrophilic/hydrophobic or ion exchange properties, or through their rentention abilities, due to pore size.     

Liquid-liquid extraction of uranium(VI) from aqueous acidic solutions using Alamine, TBP and CYANEX systems

Liquid-liquid extraction of uranium(VI) (UO₂ ²⁺) from aqueous acidic (HCl and HNO₃) solutions into a co-existing organic phase containing Alamine 308 (triisooctyl amine), TBP (tri-n-butyl phosphate) or CYANEX 302 (bis(2,4,4-trimethylpentyl) monothiophosphinic acid) and diluent (toluene) was studied at isothermal conditions (298.2 K) at aqueous phase acidity varying in the range 0.5-6 mol/dm³. All solvent systems exhibit a maximum distribution ratio restricted in the acidity range 3-4 mol/dm³. An obvious difference in extraction behavior through amine system has been observed for two acids, HCl and HNO₃, distinguishing the divergent interactions attributed to the different mechanism of complexation depending on the acidic medium. The high degree of separation of UO₂ ²⁺ from HNO₃ solution is feasible through a complex formation with extractants ranging in the order CYANEX 302 > TBP > Alamine 308. The results were correlated using various versions of the mass action law, i.e., a chemodel approach and a modified version of the Langmuir equilibrium model comprising the formation of one or at least two U(VI)-extractant aggregated structures.