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1.
Lactic acid is an important commercial product and extracting it out of aqueous solution is a growing requirement in fermentation based industries and recovery from waste streams. The design of an amine extraction process requires (i) equilibrium and (ii) kinetic data for the acid-amine (solvent) system used. Equilibria for lactic acid extraction by alamine 336 in methyl-iso-butyl-ketone (MIBK) as a diluent have been determined. The extent to which the organic phase (amine +MIBK) may be loaded with lactic acid is expressed as a loading ratio, z=[HL](o)/[B](i,o). Calculations based on the stoichiometry of the reactive extraction and the equilibria involved indicated that more lactic acid is transferred to the organic phase than would be expected from the (1:1) stoichiometry of the reaction. The extraction equilibrium was interpreted as a result of consecutive formation of two acid-amine species with stoichiometries of 1:1 and 2:1. Equilibrium complexation constant for (1:1) and (2:1) has been estimated. Kinetics of extraction of lactic acid by alamine 336 in MIBK has also been determined. In a first study of its kind, the theory of extraction accompanied by a chemical reaction has been used to obtain the kinetics of extraction of lactic acid by alamine 336 in MIBK. The reaction between lactic acid and alamine 336 in MIBK in a stirred cell falls in Regime 3, extraction accompanied by a fast chemical reaction occurring in the diffusion film. The reaction has been found to be zero order in alamine 336 and first order in lactic acid with a rate constant of 1.38 s(-1). These data will be useful in the design of extraction processes. 相似文献
2.
The reactive extraction of succinic acid was carried out by mixed tertiary amine which consisted of tripropylamine (TPA) and trioctylamine (TOA) as the extraction agent in 1-octanol/n-heptane diluent. Maximum distribution coefficient was obtained at 8:2 weight ratio of TPA/TOA. At this ratio, its extraction efficiency is above 90% at the 3.9 wt.% of succinic acid in aqueous solution. Furthermore, the prevention of the third phase formation made the phase separation between organic phase and aqueous phase easy. 相似文献
3.
Kinetic studies for the extraction of succinic acid from aqueous solution with 1-octanol solutions of tri-n-octylamine (TOA) were carried out using a stirred cell with a microporous hydrophobic membrane. The interfacial concentrations of species were correlated and thus the intrinsic kinetics was obtained. The overall extraction process was controlled by the chemical reaction at or near the interface between the aqueous and organic phases. The formation reaction of succinic acid-TOA complex was found to be first order with respect to the concentration of succinic acid in the aqueous phase and the order of 0.5 with respect to that of TOA in the organic phase with a rate constant of (3.14 +/- 0.6) x 10(-8) m(2.5) x mol(-0.5) x s(-1). The dissociation reaction of succinic acid-TOA complex was found to be the second-order with respect to that of succinic acid-TOA complex in the organic phase and the order of -2 with respect to that of TOA in the organic phase with a rate constant of (1.44 +/- 1.4) x 10(-4) mol x m(-2) x s(-1). 相似文献
4.
Biotechnologically produced succinic acid has the potential to displace maleic acid and its uses. Therefore, it is of high interest for the chemical, pharmaceutical, and food industry.In addition to optimized production strains and fermentation processes, an efficient separation of succinic acid from the aqueous fermentation broth is indispensable to compete with the current petrochemical production of succinic acid. Isolation and purification of succinic acid from an Escherichia coli fermentation broth were studied with two amine-based reactive extraction systems: (i) trihexylamine in 1-octanol and (ii) diisooctylamine and dihexylamine in a mixture of 1-octanol and 1-hexanol. Back extraction of succinic acid from the organic phase was carried out using an aqueous trimethylamine solution. The trimethylammonium succinate generated after back extraction was split with an evaporation-based crystallization.The focus was on process integration, for example, reuse of the applied amines for extraction and back extraction. It was shown that the maximum trimethylamine concentration for back extraction should not exceed the stoichiometric amount (2 mol trimethylamine/mol the succinic acid in the organic phase) to ensure maximal extraction yields with the reused organic phase in subsequent extractions. Moreover, mixer-settler extraction and back extraction of succinic acid were scaled up from the milliliter- to the liter-scale making use of liquid–liquid centrifuges. The overall yield was 83.5% of the succinic acid from thefermentation supernatant. The final purity of the succinic acid crystals was 99.5%. Organic phase and amines can easily be recycled and reused. 相似文献
5.
Biotechnologically produced succinic acid has the potential to displace maleic acid and its uses and to become an important
feedstock for the chemical industry. In addition to optimized production strains and fermentation processes, an efficient
separation of succinic acid from the aqueous fermentation broth is indispensable to compete with the current petrochemical
production processes. In this context, high molecular weight amines are known to be effective extractants for organic acids.
For this reason, as a first step of isolation and purification, the reactive extraction of succinic acid was studied by mixing
aqueous succinic acid solutions with 448 different amine–solvent mixtures as extraction agents (mixer-settler studies). The
extraction agents consist either of one amine and one solvent (208 reactive extraction systems) or two amines and two solvents
(240 reactive extraction systems). Maximum extraction yields of succinic acid from an aqueous solution with 423 mM succinic
acid at pH 2.0 were obtained with more than 95% yield with trihexylamine solved in 1-octanol or with dihexylamine and diisooctylamine
solved in 1-octanol and 1-hexanol. Applying these optimized reactive extraction systems with Escherichia coli fermentation broth resulted in extraction yields of 78–85% due to the increased ionic strength of the fermentation supernatant
and the co-extraction of other organic acids (e.g., lactic acid and acetic acid), which represent typical fermentation byproducts. 相似文献
6.
Macromolecular solvation energies derived from small molecule crystal morphology. 总被引:1,自引:1,他引:0
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The morphology of small molecule crystals provides a model for evaluating surface solvation energies in a system with similar packing density to that observed for amino acid residues in proteins. The solvation energies associated with the transfer of methylene and carboxyl groups between vacuum and aqueous phases are estimated to be approx. $40 and -260 cal/A2, respectively, from an analysis of the morphology of succinic acid crystals. These solvation energies predict values for contact angles in reasonable agreement with measurements determined from macroscopic monolayer surfaces. Transfer free energies between vapor and water phases for a series of carboxylic acids are also predicted reasonably well by these solvation energies, provided the surface exposure of different groups is quantitated with the molecular surface area rather than the more traditional accessible surface area. In general, molecular surfaces and molecular surface areas are seen to have important advantages for characterizing the structure and energetics of macromolecular surfaces. Crystal faces of succinic acid with the lowest surface energies in aqueous solution are characteristically smooth. Increasing surface roughness and apolarity are associated with higher surface energies, which suggests an approach for modifying the surface properties of proteins and other macromolecules. 相似文献
7.
Lactic acid extraction was carried out with trioctyl amine (TOA) in three diluents. The effect of initial lactic acid concentrations on the extraction efficiency was investigated. It was observed that although the percentage extraction remained constant or decreased but the loading ratio was increased in all the cases. The overloading was observed in the case of TOA in methyl isobutyl ketone (MIBK). The extraction of lactic acid was favored at a lower aqueous pH?in all the diluents. The improvement of the extraction efficiency at a higher aqueous pH?(=?6) was achieved by using the modified TOA (treated with HCl) in MIBK. However, the recovery of lactic was very poor in the case of modified TOA in MIBK, although the complete recovery was obtained for untreated TOA. 相似文献
8.
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. 相似文献
9.
Yeon Ki Hong Won Hi Hong Yong Keun Chang 《Biotechnology and Bioprocess Engineering》2001,6(5):347-351
A study was made on the extraction equilibria of succinic and formic acids from aqueous solutions using tri-n-octylamine (TOA)
in 1-octanol. It was shown that the loading values of TOA decreased with increasing pH values. The apparent equilibrium constants
for each acid-amine complex were determined by an equilibrium model. In the case of succinic acid, the formation of a bisuccinate
anion played an important role in the stoichiometry of the acid-amine complex. 相似文献
10.
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. 相似文献
11.
Sushil Kumar B. V. Babu Kailas L. Wasewar 《Biotechnology and Bioprocess Engineering》2012,17(6):1252-1260
This paper presents the reactive extraction of propionic acid from aqueous solution by amine based extractants such as tri-n-octylamine and Aliquat 336, dissolved in a mixture of n-dodecane and 1-decanol. Equilibrium experiments were carried out to investigate the effects of various parameters such as modifier (1-decanol) concentration, extractant type, extractant composition, diluent composition, and initial acid concentration on the extraction efficiency. The extraction efficiency was found to be increased with an increase in modifier composition and extractant composition, and decreased with increases in initial acid concentration. Different biocompatible extractant/diluent systems such as (1) 20% TOA, 20% 1-decanol and 60% n-dodecane, (2) 20% TOA, 30% 1-decanol and 50% n-dodecane, (3) 30% TOA, 20% 1-decanol and 50% n-dodecane and (4) 25% Aliquat 336, 25% 1-decanol and 50% n-dodecane are developed and used in this study. A mathematical model based on mass action law and a population-based search algorithm (differential evolution, DE) is proposed, and is used to estimate the extraction equilibrium constant (K E) and stoichiometry of reactive extraction. Individual equilibrium constants for the simultaneous formation of (1:1) and (2:1) acid:amine complexes are also determined. The extraction system comprised of 20% TOA, 30% 1-decanol, and 50% n-dodecane was found to be the best among the four biocompatible extractant/diluent systems studied. The loading ratios found in the range of 0.113 ~ 1.05 indicated the simultaneous formation of 1:1 and 2:1 complexes between acid and TOA. 相似文献
12.
A simple procedure for removing methacrylic acid from water-miscible methacrylates is described. One volume of monomer is diluted with 9 volumes of diethyl ether. Three consecutive extractions are carried out with 5% aqueous NaHCO3 at 4 C. Residual water is removed by shaking with anhydrous sodium sulfate. The ether is removed by flash evaporation on a Biichi Rotavapor. Weak alkali extraction produces good quality semithin sections which are free of background staining. This method may be a useful alternative to existing methods for removal of methacrylic acid. 相似文献
13.
Crans DC Baruah B Gaidamauskas E Lemons BG Lorenz BB Johnson MD 《Journal of inorganic biochemistry》2008,102(5-6):1334-1347
The anti-oxidant properties of L-ascorbic acid were investigated in the confined medium produced by a sodium bis(2-ethylhexyl)sulfosuccinate (aerosol-OT, AOT) self-assembled reverse micelle. Using 1H-1H NOESY (proton-proton 2D nuclear overhauser enhancement correlation spectroscopy) NMR spectroscopy, the location of ascorbic acid was investigated and found to be at the AOT-interface in contrast to earlier studies where the ascorbate was assumed to be in the water pool in these microemulsions. The reaction of ascorbic acid with oxygen was investigated using EPR spectroscopy. A delocalized monoanionic ascorbate radical was observed in microemulsions prepared from pH 5.6 stock solutions. This is in contrast to studies carried out in aqueous media where no radical formation was observed. The oxidation of ascorbic acid by aqueous V(V) was investigated in reverse micelles. Modest changes in the kinetic parameters were observed for this system compared to that in water. Details of these reactions were examined and can be summarized as the microemulsion solvating and stabilizing reactive intermediates via rate inhibition or enhancement. The inhibition of the oxidation is due to solvation stabilization of ascorbic acid in microemulsion media. Since ascorbate is a valuable marker of oxidative stress, our results suggest that compartmentization can modify the stabilization of the ascorbate radical and the changes in properties could be important in biological systems. 相似文献
14.
Continuum solvation models that estimate free energies of solvation as a function of solvent accessible surface area are computationally simple enough to be useful for predicting protein conformation. The behavior of three such solvation models has been examined by applying them to the minimization of the conformational energy of bovine pancreatic trypsin inhibitor. The models differ only with regard to how the constants of proportionality between free energy and surface area were derived. Each model was derived by fitting to experimentally measured equilibrium solution properties. For two models, the solution property was free energy of hydration. For the third, the property was NMR coupling constants. The purpose of this study is to determine the effect of applying these solvation models to the nonequilibrium conformations of a protein arising in the course of global searches for conformational energy minima. Two approaches were used: (1) local energy minimization of an ensemble of conformations similar to the equilibrium conformation and (2) global search trajectories using Monte Carlo plus minimization starting from a single conformation similar to the equilibrium conformation. For the two models derived from free energy measurements, it was found that both the global searches and local minimizations yielded conformations more similar to the X-ray crystallographic structures than did searches or local minimizations carried out in the absence of a solvation component of the conformational energy. The model derived from NMR coupling constants behaved similarly to the other models in the context of a global search trajectory. For one of the models derived from measured free energies of hydration, it was found that minimization of an ensemble of near-equilibrium conformations yielded a new ensemble in which the conformation most similar to the X-ray determined structure PTI4 had the lowest total free energy. Despite the simplicity of the continuum solvation models, the final conformation generated in the trajectories for each of the models exhibited some of the characteristics that have been reported for conformations obtained from molecular dynamics simulations in the presence of a bath of explicit water molecules. They have smaller root mean square (rms) deviations from the experimentally determined conformation, fewer incorrect hydrogen bonds, and slightly larger radii of gyration than do conformations derived from search trajectories carried out in the absence of solvent. 相似文献
15.
The kinetics and mechanisms of the reaction of iron(III) with gallic acid, gallic acid methyl ester and catechin. 总被引:1,自引:0,他引:1
The kinetics and mechanisms of the reactions of a number of pyrogallol-based ligands with iron(III) have been investigated in aqueous solution at 25 degrees C and ionic strength 0.5 M NaClO(4). Mechanisms have been proposed which account satisfactorily for the kinetic data. These are generally consistent with a mechanism in which the 1:1 complex that is formed initially when the metal reacts with the ligand subsequently decays through an electron transfer reaction. There was also some evidence for the formation of a 1:2 ligand-to-metal complex at higher pH values. The kinetics of complex formation were investigated with either the ligand or metal in pseudo-first-order excess. Rate constants for k(1) of 2.83(+/-0.09)x10(3), 1.75(+/-0.045)x10(3) and 3300(+/-200) M(-1) s(-1) and k(-1) of 20(+/-6.0), 35(+/-13) and 25+/-7.6 M(-1) s(-1) have been evaluated for the reaction of Fe(OH)(2+) with gallic acid, gallic acid methyl ester and catechin, respectively. The stability constant of each [Fe(L)](+) complex has been calculated from the kinetic data. The iron(III) assisted decomposition of the initial iron(III) complex formed was investigated. Analysis of the kinetic data yielded both the equilibrium constants for protonation of the iron(III) complexes initially formed together with the rate constants for the intramolecular electron transfers for gallic acid and gallic acid methyl ester. All of the suggested mechanisms and calculated rate constants are supported by calculations carried out using global analysis of time-dependent spectra. 相似文献
16.
17.
Batch sorption experiments were carried out for removal of malachite green from aqueous solution using pretreated rice husk. The equilibrium kinetic data were analyzed using pseudo-second-order kinetic model. A comparison between linear and nonlinear methods of estimating the kinetic parameters was carried out. Four pseudo-second-order kinetic linear equations were discussed. The coefficient of determination (r 2) and chi-square (χ2) test were employed as error analysis methods to determine the best-fitting equation. The results show that nonlinear method is a better alternative to obtain the kinetic parameters. In addition, the chi-square test was a better method to determine the best-fitting model. 相似文献
18.
F. J. van Bemmelen M. J. Schouten D. Fekkes J. Bruinvels 《Journal of neurochemistry》1985,45(5):1471-1474
The conversion of succinic semialdehyde into gamma-aminobutyric acid (GABA) by GABA-transaminase was measured in rat brain homogenate in the presence of different concentrations of the cosubstrate glutamate. The calculated kinetic parameters of succinic semialdehyde for GABA-transaminase were a limiting Km value of 168 microM and a limiting Vmax value of 38 mumol g-1 h-1. Combination with previously obtained data for the conversion of GABA into succinic semialdehyde revealed a kEq value of 0.04, indicating that equilibrium of GABA-transaminase is biased toward the formation of GABA. The increased formation of GABA in the presence of succinic semialdehyde was not due to an increased conversion of glutamate into GABA by glutamic acid decarboxylase. Therefore these results indicate that succinic semialdehyde can act as a precursor for GABA synthesis. 相似文献
19.
Coir pith was chemically modified for the adsorption of cobalt(II) ions from aqueous solution. Chemical modification was done by esterification using succinic anhydride followed by activation with NaHCO(3) in order to improve the adsorption of Co(II). Adsorptive removal of Co(II) from aqueous solution onto modified coir pith was evaluated in batch studies under varying conditions of agitation time and metal ion concentration to assess the kinetic and equilibrium parameters. A pseudo-second-order kinetic model fitted well for the sorption of Co(II) onto modified coir pith. Sorption kinetics showed that the loading of Co(II) by this material was quite fast under ambient conditions. The Langmuir and Freundlich equilibrium isotherm models provided excellent fits for the adsorption data, with R(2) of 0.99 and 0.98, respectively. After esterification, the maximum Co(II) sorption loading Q(0); was greatly improved. It is evident that chemically modified adsorbent exhibits better Co(II) removal capability than raw adsorbent suggesting that surface modification of the adsorbent generates more adsorption sites on its solid surface for metal adsorption. A complete recovery of the adsorbed metal ions from the spent adsorbent was achieved by using 1.0N HCl. 相似文献
20.
Debbie C. Crans Bharat Baruah Ernestas Gaidamauskas Brant G. Lemons Bret B. Lorenz Michael D. Johnson 《Journal of inorganic biochemistry》2008,102(5-6):1334
The anti-oxidant properties of l-ascorbic acid were investigated in the confined medium produced by a sodium bis(2-ethylhexyl)sulfosuccinate (aerosol-OT, AOT) self-assembled reverse micelle. Using 1H–1H NOESY (proton-proton 2D nuclear overhauser enhancement correlation spectroscopy) NMR spectroscopy, the location of ascorbic acid was investigated and found to be at the AOT-interface in contrast to earlier studies where the ascorbate was assumed to be in the water pool in these microemulsions. The reaction of ascorbic acid with oxygen was investigated using EPR spectroscopy. A delocalized monoanionic ascorbate radical was observed in microemulsions prepared from pH 5.6 stock solutions. This is in contrast to studies carried out in aqueous media where no radical formation was observed. The oxidation of ascorbic acid by aqueous V(V) was investigated in reverse micelles. Modest changes in the kinetic parameters were observed for this system compared to that in water. Details of these reactions were examined and can be summarized as the microemulsion solvating and stabilizing reactive intermediates via rate inhibition or enhancement. The inhibition of the oxidation is due to solvation stabilization of ascorbic acid in microemulsion media. Since ascorbate is a valuable marker of oxidative stress, our results suggest that compartmentization can modify the stabilization of the ascorbate radical and the changes in properties could be important in biological systems. 相似文献