The effect of raw glycerol concentration on the production of 1,3‐propanediol by Clostridium butyricum

Raw glycerol, the main by‐product of the bio‐diesel production process, was converted to 1,3‐propanediol by Clostridium butyricum F2b. In batch cultures, 47.1 g dm^?3 of 1,3‐propanediol were produced. Continuous cultures were conducted at a constant dilution rate (= 0.04 h^?1) and various inlet glycerol concentrations with 1,3‐propanediol produced at levels up to 44.0 g dm^?3. At increasing glycerol concentrations in the inlet medium, biomass yield decreased. This decrease was attributed to the microbial metabolism being directed towards the biosynthesis of organic acids (and hence carbon losses as CO₂) instead of biochemical anabolic reactions. An autonomous analytical model was developed, and quantified the effect of inlet glycerol concentration on the production of biomass and metabolites. Indeed, high inlet substrate concentrations positively affected the biosynthesis, principally of butyric acid and to a lesser extent that of acetic acid. In contrast, at increased glycerol concentrations, the relative increase of 1,3‐propanediol production per unit of substrate consumed was lower as compared with that of acetic and, mainly, butyric acid. This could be explained by the fact that the butyric acid pathway represents an alternative and competitive one to that of 1,3‐propanediol for re‐generation of NADH₂ equivalents in the microbial cell. Copyright © 2004 Society of Chemical Industry     

Over‐expression of glycerol dehydrogenase and 1,3‐propanediol oxidoreductase in Klebsiella pneumoniae and their effects on conversion of glycerol into 1,3‐propanediol in resting cell system

BACKGROUND: Glycerol dehydrogenase [EC.1.1.1.6] and 1,3‐propanediol oxidoreductase [EC.1.1.1.202] were proved to be two of the key enzymes for glycerol conversion to 1,3‐propanediol in Klebsiella pneumoniae under anaerobic conditions. For insight into their significance on 1,3‐propanediol production under micro‐aerobic conditions, these two enzymes were over‐expressed in K. pneumoniae individually, and their effects on conversion of glycerol into 1,3‐propanediol in a resting cell system under micro‐aerobic conditions were investigated. RESULTS: In the resting cell system, over‐expression of 1,3‐propanediol oxidoreductase led to faster glycerol conversion and 1,3‐propanediol production. After a 12 h conversion process, it improved the yield of 1,3‐propanediol by 20.4% (222.1 mmol L⁻¹ versus 184.4 mmol L⁻¹) and enhanced the conversion ratio of glycerol into 1,3‐propanediol from 50.8% to 59.8% (mol mol⁻¹). Over‐expression of glycerol dehydrogenase in K. pneumoniae had no significant influence both on 1,3‐propanediol yield and on the conversion ratio of glycerol into 1,3‐propanediol in the resting cell system. CONCLUSION: The results were important for an understanding of the significance of glycerol dehydrogenase and 1,3‐propanediol oxidoreductase in 1,3‐proanediol production under micro‐aerobic conditions, and for developing better strategies to improve 1,3‐propanediol yield. Copyright © 2008 Society of Chemical Industry     

Synergistic extraction of rare earths(III) from chloride medium with mixtures of 1‐phenyl‐3‐methyl‐4‐benzoyl‐pyrazalone‐5 and di‐(2‐ethylhexyl)‐2‐ethylhexylphosphonate

The synergistic effect of 1‐phenyl‐3‐methyl‐4‐benzoyl‐pyrazalone‐5 (HPMBP, HA) and di‐(2‐ethylhexyl)‐2‐ethylhexylphosphonate (DEHEHP, B) in the extraction of rare earths (RE) from chloride solutions has been investigated. Under the experimental conditions used, there was no detectable extraction when DEHEHP was used as a single extractant while the amount of RE(III) extracted by HPMBP alone was also low. But mixtures of the two extractants at a certain ratio had very high extractability for all the RE(III). For example, the synergistic enhancement coefficient was calculated to be 9.35 for Y³⁺, and taking Yb³⁺ and Y³⁺ as examples, RE³⁺ is extracted as RE(OH)A₂.B. The stoichiometry, extraction constants and thermodynamic functions such as Gibbs free energy change ΔG (?17.06 kJ mol^?1), enthalpy change ΔH (?35.08 kJ mol^?1) and entropy change ΔS (?60.47 J K^?1 mol^?1) for Y³⁺ at 298 K were determined. The separation factors (SF) for adjacent pairs of rare earths were calculated. Studies show that the binary extraction system not only enhances the extraction efficiency of RE(III) but also improves the selectivity, especially between La(III) and the other rare earth elements. Copyright © 2006 Society of Chemical Industry     

Synthesis of glycerol carbonate by direct carbonatation of glycerol in supercritical CO2 in the presence of zeolites and ion exchange resins

Glycerol carbonate is a key bifunctional compound employed as solvent, additive, monomer, and chemical intermediate. We have synthesized it on a pilot scale in the laboratory in cyclic or alicyclic organic carbonate medium. In this study, we examined the use of supercritical CO₂ as a reaction medium and as a source of carbonate for carbonatation of glycerol. Glycerol carbonate could be obtained by direct reaction of carbon dioxide with an organic carbonate in the presence of heterogeneous catalysts. Carbonatation of glycerol into glycerol carbonate went to equilibrium in supercritical CO₂ medium. This revised version was published online in July 2006 with corrections to the Cover Date.     

Extraction and separation of rare earths from chloride medium with mixtures of 2‐ethylhexylphosphonic acid mono‐(2‐ethylhexyl) ester and sec‐nonylphenoxy acetic acid

BACKGROUND: 2‐ethylhexylphosphonic acid mono‐(2‐ethylhexyl) ester (HEHEHP, H₂A₂) has been applied extensively to the extraction of rare earths. However, there are some limitations to its further utilization and the synergistic extraction of rare earths with mixtures of HEHEHP and another extractant has attracted much attention. Organic carboxylic acids are also a type of extractant employed for the extraction of rare earths, e.g. naphthenic acid has been widely used to separate yttrium from rare earths. Compared with naphthenic acid, sec‐nonylphenoxy acetic acid (CA100, H₂B₂) has many advantages such as stable composition, low solubility, and strong acidity in the aqueous phase. In the present study, the extraction of rare earths with mixtures of HEHEHP and CA100 has been investigated. The separation of the rare earth elements is also studied. RESULTS: The synergistic enhancement coefficient decreases with increasing atomic number of the lanthanoid. A significant synergistic effect is found for the extraction of La³⁺ as the complex LaH₂ClA₂B₂ with mixtures of HEHEHP and CA100. The equilibrium constant and thermodynamic functions obtained from the experimental results are 10^?0.92 (K_AB), 13.23 kJ mol^?1 (ΔH), 5.25 kJ mol^?1 (ΔG), and 26.75 J mol^?1 K^?1 (ΔS), respectively. CONCLUSION: Graphical and numerical methods have been successfully employed to determine the stoichiometries for the extraction of La³⁺ with mixtures of HEHEHP and CA100. The mixtures have different extraction effects on different rare earths, which provides the possibility for the separation of yttrium from heavy rare earths at an appropriate ratio of HEHEHP and CA100. Copyright © 2009 Society of Chemical Industry     

Precipitation polymerization of acrylamide with quaternary ammonium cationic monomer in potassium carbonate solution initiated by plasma

Precipitation polymerization of 2‐(methacryloyloxyethyl) trimethyl ammonium chloride (DMC)‐co‐acrylamide (AM) [poly(AM‐DMC)] has been successfully performed in potassium carbonate (K₂CO₃)‐water media by plasma initiation. K₂CO₃ solution was selected because not only the higher solubility of AM and DMC comparing with that of poly(AM‐DMC), but the higher intrinsic viscosity of poly(AM‐DMC) could be obtained. A set of experiments was performed using different K₂CO₃ concentration (from 50 down to 10% (w/w)), thus the precipitation architecture was not obtained below 20% (w/w). And particles size, particles size distribution (7–120 μm), and intrinsic viscosity of poly(AM‐DMC) (ranging up to 455 cm³/g) were also summarized in this article. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4060–4067, 2007     

Pre‐treatment and utilization of raw glycerol from sunflower oil biodiesel for growth and 1,3‐propanediol production by Clostridium butyricum

BACKGROUND: The objective of the present work is to report an efficient pre‐treatment process for sunflower oil biodiesel raw glycerol (SOB‐RG) and its fermentation to 1,3‐propanediol. RESULTS: The growth inhibition percentages of Clostridium butyricum DSM 5431 on grade A (pH 4.0) and grade B (pH 5.0) phosphoric acid‐treated SOB‐RG were similar to those of pure glycerol at 20 g glycerol L^?1; i.e., 18.5 ± 0.707% to 20.5 ± 0.7% inhibition. In grade A, growth inhibition was reduced from 85.25 ± 0.35% to 32 ± 1.4% (a 53.25% reduction) at 40 g glycerol L^?1 by washing grade A raw glycerol twice with n‐hexanol (grade A‐2). The kinetic parameters for product formation and substrate consumption in anaerobic batch cultures gave almost similar values at 20 g glycerol L^?1, while at 50 g glycerol L^?1 volumetric productivity (Q_p) and specific rate of 1,3‐propanediol formation (q_p) were improved from 1.13 to 1.85 g L^?1 h^?1 and 1.60 to 2.65 g g^?1 h^?1, respectively, by employing grade A‐2 raw glycerol, while the yields were similar (0.5–0.52 g g^?1). CONCLUSION: The results are important as the pre‐treatment of SOB‐RG is necessary to develop bioprocess technologies for conversion of SOB‐RG to 1,3‐propanediol. Copyright © 2008 Society of Chemical Industry     

Microwave‐assisted synthesis of polyglycerol from glycerol carbonate

Microwave irradiation of glycerol carbonate allows formation of glycidol, which readily polymerizes to form polyglycerol under mild conditions comparatively to the classical polyetherification reaction involving high temperature and basic conditions. Analysis of the crude reactional mixture indicated the presence of low‐molecular weight oligomers constituted mainly of di, tri, and tetraglycerols with small quantities of higher molecular weights oligomers. Molecular size distribution was relatively similar to that of polyglycerols obtained under basic condition, even if these latter contained slightly higher amounts of high‐molecular weight oligomers. Structure of oligomers differs slightly according to the conditions of polymerization, and polyglycerols are obtained under microwave activation containing higher contents of cyclic isomers, whereas polyglycerols obtained under basic conditions contain more ramified isomers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reaction kinetics of 2‐((2‐aminoethyl) amino) ethanol in aqueous and non‐aqueous solutions using the stopped‐flow technique

Observed pseudo‐first‐order rate constants (k_o) for the reaction between CO₂ and 2‐((2‐aminoethyl) amino) ethanol (AEEA) were measured using the stopped‐flow technique in an aqueous system at 298, 303, 308 and 313 K, and in non‐aqueous systems of methanol and ethanol at 293, 298, 303 and 308 K. Alkanolamine concentrations ranged from 9.93 to 80.29 mol m^?3 for the aqueous system, 29.99–88.3 mol m^?3 for methanol and 44.17–99.28 mol m^?3 for ethanol. Experimentally obtained rate constants were correlated with two mechanisms. For both the aqueous‐ and non‐aqueous‐AEEA systems, the zwitterion mechanism with a fast deprotonation step correlated the data well as assessed by the reported statistical analysis. As expected, the reaction rate of CO₂ in the aqueous‐AEEA system was found to be much faster than in methanol or ethanol. Compared to other promising amines and diamines studied using the stopped‐flow apparatus, the pseudo‐first‐order reaction rate constants were found to obey the following order: PZ (cyclic‐diamine) > EDA (diamine) > AEEA (diamine) > 3‐AP (primary amine) > MEA (primary amine) > EEA (primary amine) > MO (cyclic‐amine). The reaction rate constant of CO₂ in aqueous‐AEEA was double that in aqueous‐MEA, and the difference increased with an increase in concentration. All reaction orders were practically unity. With a higher capacity for carbon dioxide and a higher reaction rate, AEEA could have been a good substitute to MEA if not for its high thermal degradation. AEEA kinetic behaviour is still of interest as a degradation product of MEA. © 2012 Canadian Society for Chemical Engineering     

Syntheses and adsorption properties for Hg2+ of chelating resin of crosslinked polystyrene‐supported 2,5‐dimercapto‐1,3,4‐thiodiazole

A novel chelating resin with functional group containing S and N atoms was prepared using chloromethylated polystyrene and 2,5‐dimercapto‐1,3,4‐thiodiazole (also called bismuththiol I, BMT) as materials. Its structure was characterized by infrared spectra and elementary analysis. The results showed that the content of the functional group was 2.07 mmol BMT g^?1 resin, 47% of which were in the form of monosubstitution (PS‐BMT‐1) and 53% in the form of double substitution (PS‐BMT‐2). The adsorption for mercury ion was investigated. The adsorption dynamics showed that the adsorption was controlled by liquid film diffusion. Increasing the temperature was beneficial to adsorption. The Langmuir model was much better than the Freundlich model to describe the isothermal process. The adsorption activation energy (E_a), ΔG, ΔH, and ΔS values calculated were 18.56 kJ·mol^?1, ‐5.99 kJ·mol^?1, 16.38 kJ·mol^?1, and 37.36, J·mol^?1·K^?1, respectively. The chelating resin could be easily regenerated by 2% thiourea in 0.1 mol·L^?1 HCl with higher effectiveness. Five adsorption–desorption cycles demonstrated that this resin was suitable for repeated use without considerable change in adsorption capacity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1646–1652, 2004     

Electrochemical synthesis of dimethyl carbonate from methanol,CO2 and propylene oxide in an ionic liquid

BACKGROUND: Dimethyl carbonate (DMC) can be used effectively as an environmentally benign substitute for highly toxic phosgene and dimethyl sulfate in carbonylation and methylation, as well as a promising octane booster owing to its high oxygen content. Two‐step transesterification from epoxide, methanol, and CO₂ is widely used in the bulk production of DMC. However, major disadvantages of this process are high energy consumption, and high investment and production costs. A one pot synthesis of DMC from carbon dioxide, methanol, and epoxide was, therefore, developed. But the yields of DMC are below 70% due to the thermodynamic limitation. RESULTS: Electrochemical synthesis of DMC was conducted with platinum electrodes from methanol, CO₂ and propylene oxide in an ionic liquid was conducted. The bmimBr (1‐butyl‐3‐methylimidazolium bromide)‐methanol‐propylene oxide system with CO₂ bubbling allows DMC to be effectively synthesized and a high yield (75.5%) was achieved. CONCLUSION: In this electrolysis, redox reactions of substrates, CO₂, methanol, and propylene oxide, on Pt electrodes were carried out, producing the activated particles, CH₃O^?, CH₃OH⁺, CO₂^? and PO^?, resulting in the effective synthesis of DMC with a 75.5% yield in an ionic liquid (bmimBr). Finally, a mechanism for this synthesis reaction was proposed, which is very different from those reported in the literature. Copyright © 2011 Society of Chemical Industry     

Strain isolation and optimization of process parameters for bioconversion of glycerol to lactic acid

BACKGROUND: The crude glycerol from biodiesel production represents an abundant and inexpensive source which can be used as raw material for lactic acid production. The first aim of this investigation was to select a strain suitable for producing lactic acid from glycerol with a high concentration and productivity. The second aim was to obtain the optimum fermentation conditions, as a basis for large‐scale lactate production in the future. RESULTS: Eight bacterial strains, which could aerobically convert glycerol to lactic acid, were screened from soil samples. One of the strains, AC‐521, which synthesized lactic acid with a higher concentration, was identified based on its 16S rDNA sequences and physiological characteristics. These results indicated that this strain was a member of Escherichia coli. The optimal fermentation conditions for Escherichia coli AC‐521 were 42 °C, pH 6.5, 0.85 min^?1 (K_La). CONCLUSION: Escherichia coli AC‐521 suitable for producing lactic acid from glycerol with high concentration and productivity was identified. After 88 h of fed‐batch fermentation, both the lactic acid concentration and glycerol consumption reached maximum, giving 85.8 g L^?1 of lactic acid with a productivity of 0.97 g L^?1 h^?1 and a yield of 0.9 mol mol^?1 glycerol. Copyright © 2009 Society of Chemical Industry     

Synthesis and biological activity of medium range molecular weight polymers containing exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidocaproic acid

A new monomer, exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidocaproic acid (ETCA), was prepared by reaction of maleimidocaproic acid and furan. The homopolymer of ETCA and its copolymers with acrylic acid (AA) or with vinyl acetate (VAc) were obtained by photopolymerizations using 2,2‐dimethoxy‐2‐phenylacetophenone as an initiator at 25 °C. The synthesized ETCA and its polymers were identified by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The apparent average molecular weights and polydispersity indices determined by gel permeation chromatography (GPC) were as follows: M_n = 9600 g mol^?1, M_w = 9800 g mol^?1, M_w/M_n = 1.1 for poly(ETCA); M_n = 14 300 g mol^?1, M_w = 16 200 g mol^?1, M_w/M_n = 1.2 for poly(ETCA‐co‐AA); M_n = 17 900 g mol^?1, M_w = 18 300 g mol^?1, M_w/M_n = 1.1 for poly(ETCA‐co‐VAc). The in vitro cytotoxicity of the synthesized compounds against mouse mammary carcinoma and human histiocytic lymphoma cancer cell lines decreased in the following order: 5‐fluorouracil (5‐FU) ≥ ETCA > polymers. The in vivo antitumour activity of the polymers against Balb/C mice bearing sarcoma 180 tumour cells was greater than that of 5‐FU at all doses tested. © 2001 Society of Chemical Industry     

Synthesis and biological activity of phthalimide‐based polymers containing 5‐fluorouracil

The attachment of anticancer agents to polymers is a promising approach towards reducing the toxic side‐effects and retaining the potent antitumour activity of these agents. A new tetrahydrophthalimido monomer containing 5‐fluorouracil (ETPFU) and its homopolymer and copolymers with acrylic acid (AA) and with vinyl acetate (VAc) have been synthesized and spectroscopically characterized. The ETPFU contents in poly(ETPFU‐co‐AA) and poly(ETPFU‐co‐VAc) obtained by elemental analysis were 21 mol% and 20 mol%, respectively. The average molecular weights of the polymers determined by gel permeation chromatography were as follows: M_n = 8900 g mol^?1, M_w = 13 300 g mol^?1, M_w/M_n = 1.5 for poly(ETPFU); M_n = 13 500 g mol^?1, M_w = 16 600 g mol^?1, M_w/M_n = 1.2 for poly(ETPFU‐co‐AA); M_n = 8300 g mol^?1, M_w = 11 600 g mol^?1, M_w/M_n = 1.4 poly(ETPFU‐co‐VAc). The in vitro cytotoxicity of the compounds against FM3A and U937 cancer cell lines increased in the following order: ETPFU > 5‐FU > poly(ETPFU) > poly(ETPFU‐co‐AA) > poly(ETPFU‐co‐VAc). The in vivo antitumour activities of all the polymers in Balb/C mice bearing the sarcoma 180 tumour cell line were greater than those of 5‐FU and monomer at the highest dose (800 mg kg^?1). © 2002 Society of Chemical Industry     

Catalytic synthesis of toluene‐2,4‐diisocyanate from dimethyl carbonate

The process for catalytic synthesis of toluene‐2,4‐diisocyanate (TDI) from dimethyl carbonate (DMC) consists of two steps. Starting from the catalytic reaction between toluene‐2,4‐diamine (TDA) and DMC, dimethyl toluene‐2,4‐dicarbamate (TDC) is formed, and then decomposed to TDI. For the first step, the yield of TDC is 53.5% at a temperature of 250 °C, over Zn(OAc)₂/α–Al₂O₃ catalyst. For the second step, the yield of TDI is 92.6% at temperatures of 250–270 °C and under pressure of 2.7 kPa, over uranyl zinc acetate catalyst, when di‐n‐octyl sebacate(DOS) is used as heat‐carrier, and a mixture of tetrahydrofuran (THF) and nitrobenzene is used as solvent. © 2001 Society of Chemical Industry     

RAFT polymerization of N‐vinyl pyrrolidone using prop‐2‐ynyl morpholine‐4‐carbodithioate as a new chain transfer agent

RAFT polymerization of N‐vinyl pyrrolidone (NVP) has been investigated in the presence of chain transfer agent (CTA), i.e., prop‐2‐ynyl morpholine‐4‐carbodithioate (PMDC). The influence of reaction parameters such as monomer concentration [NVP], molar ratio of [CTA]/[AIBN, i.e., 2,2′‐azobis (2‐methylpropionitrile)] and [NVP]/[CTA], and temperature have been studied with regard to time and conversion limit. This study evidences the parameters leading to an excellent control of molecular weight and molar mass dispersity. NVP has been polymerized by maintaining molar ratio [NVP]: [PMDC]: [AIBN] = 100 : 1 : 0.2. Kinetics of the reaction was strongly influenced by both temperature and [CTA]/[AIBN] ratio and to a lesser extent by monomer concentration. The activation energy (E_a = 31.02 kJ mol^?1) and enthalpy of activation (ΔH^?= 28.29 kJ mol^?1) was in a good agreement to each other. The negative entropy of activation (ΔS^? = ?210.16 J mol^‐1K^‐1) shows that the movement of reactants are highly restricted at transition state during polymerization. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Hydrogenolysis of glycerol to 1,2‐propanediol catalyzed by Cu‐H4SiW12O40/Al2O3 in liquid phase

BACKGROUND: Crude glycerol will increase to over 400 million L year^?1, and the market is likely to become saturated due to the limited demand for glycerol. The main aim of this work is to develop a novel process for the sustainable conversion of glycerol to 1,2‐propanediol (l,2‐PD). RESULTS: Cu‐H₄SiW₁₂O₄₀/Al₂O₃ catalysts with different H₄SiW₁₂O₄₀ (STA) loadings were prepared for the hydrogenolysis of glycerol to produce l,2‐PD in liquid phase. At 513 K, 6 MPa and LHSV of 0.9 h^?1 in 10% (w/w) glycerol aqueous solutions, the catalyst with 5% (w/w) STA showed the best performance with 90.1% of glycerol conversion and 89.7% selectivity to l,2‐PD. More important, both the initial glycerol conversion and l,2‐PD selectivity were maintained over 250 h. CONCLUSION: l,2‐PD can be continuously produced with high yields via the liquid phase hydrogenolysis of glycerol over Cu‐H₄SiW₁₂O₄₀/Al₂O₃. Furthermore, the characterization indicated that catalyst acidity could be greatly modified by STA, which promoted Cu reducibility. It was also found that hydrogenolysis could be favored by a bi‐functional catalyst with the appropriate amount of both acid and metal sites. Copyright © 2010 Society of Chemical Industry     

Salting‐out of acetone, 1‐butanol,and ethanol from dilute aqueous solutions

The salting‐out phase equilibria for acetone, 1‐butanol, and ethanol (ABE) from dilute aqueous solutions using potassium carbonate (K₂CO₃) and dipotassium hydrogen phosphate trihydrate (K₂HPO₄?3H₂O) as outstanding salting‐out agents were investigated. Increasing the salt concentration strengthened the salting‐out effects and improved the distribution coefficients of all three solvents (ABE) significantly. Temperature had a slight effect on the phase equilibria. The K₂HPO₄ solution (69 wt %) showed a stronger salting‐out effect than the K₂CO₃ solution (56 wt %) on recovering ABE from dilute aqueous solutions. Dilute aqueous solutions containing more solvents increased the recoveries of acetone and 1‐butanol, while the results showed a negligible effect on the solubility of ABE. The solubility of ABE was also correlated well with the molar number of salt per gram of water in the aqueous phase. A new equation demonstrated this satisfactorily. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3470–3478, 2015     

Functionalized Ionic Liquid-Catalyzed 1-Feruloyl-sn-glycerol Synthesis

Feruloyl Glycerol (FG) is a potential antioxidant and UV absorbing ingredient in food and cosmetic industries. Transesterifications of ethyl ferulate (EF) with glycerol to synthesize FG were performed using different functionalized ionic liquids (1‐butylsulfonic‐3‐methylimidazolium tosylate, [BSO₃HMIM]TS; 1‐propylsulfonic‐3‐methylimidazolium tosylate, [PSO₃HMIM]TS; 1‐butylsulfonic‐3‐methylimidazolium trifluoromethanesulfonate, [BSO₃HMIM]OTF; 1‐butylsulfonic‐3‐methylimidazolium hydrogen sulfate, [BSO₃HMIM]HSO₄; N‐methylimidazolium hydrogen sulfate, [HMIM]HSO₄; 1‐butyl‐3‐methylimidazolium hydroxide, [BMIM]OH; 1‐butyl‐3‐methylimidazo tetrachloride molysite, [BMIM]FeCl₄; and 1‐hexyl‐3‐methylimidazo tetrachloride molysite, [BMIM]FeCl₄) as catalysts, respectively. High EF conversion (98.0 ± 1.5 %), 1‐FG (1‐feruloyl‐sn‐glycerol) yield (88.7 ± 1.1 %) and reaction selectivity for 1‐FG (90.5 ± 2.1 %) were obtained using [BSO₃HMIM]TS as catalyst. The activation energy (E_a), the Michaelis–Menten kinetic constant (K_m), and the maximum initial reaction rate (v_max) of the transesterification are 65.9 ± 3.3 kJ/mol, 1.8 ± 0.1 mol/L, and (1.6 ± 0.4) × 10^?2 mol/(L min), respectively. Effects of catalyst loading, reaction temperature, and the molar ratio of EF to glycerol on EF conversion and reaction selectivity for 1‐FG (1‐FG yield/EF conversion) were also investigated.     

Kinetic study on biphasic recognition chiral extraction for separation of α‐cyclohexyl‐mandelic acid enantiomers

BACKGROUND: Chiral solvent extraction is a potentially attractive chiral separation technique. It is essential to know the intrinsic complexation kinetics for selection, design and operation of reactive extraction equipment and for reliable scale‐up. The objective of this research is to study the kinetics of biphasic recognition chiral extraction of α‐cyclohexyl‐mandelic acid (α‐CHMA) enantiomers using a modified Lewis cell. RESULTS: The experimental results demonstrate that the extraction reaction kinetics is fast, and the reactions are first order with respect to α‐CHMA and second order with respect to D‐IBTA, with forward rate constants of 6.54 × 10^?4 mol^?2 m⁶ s^?1 for S‐α‐CHMA and 6.84 × 10^?4 mol^?2 m⁶ s^?1 for R‐α‐CHMA. With increase of HP‐β‐CD concentration in aqueous phase, enantioselectivity increases, while the overall mass transfer coefficients decrease. CONCLUSIONS: Sufficient enantioselectivity and fast kinetics of extraction can be obtained in the BRCE system at HP‐β‐CD concentration of 0.1 mol L^?1 and D‐IBTA concentration of 0.2 mol L^?1. These data will be useful in the design of extraction processes. Copyright © 2012 Society of Chemical Industry