Recovery of pyruvic acid with weakly basic polymeric sorbents

BACKGROUND: Carboxylic acids are among the most important substances that can be manufactured from biomass. However, the recovery of carboxylic acids from fermentation broths presents a challenging separation problem. To avoid the production of waste salts and net consumption of chemicals in the calcium carboxylate salt process, the use of reversible chemical complexation with polymeric sorbents and extractants is attractive for carboxylic acid recovery. Pyruvic acid is widely used in the manufacture of medicines, pesticides and foodstuffs and can be produced by fermentation. Since the acidity of pyruvic acid (pK_a = 2.49) is stronger than that of normal carboxylic acids, and as few reports on the recovery of pyruvic acid are available, the sorption of pyruvic acid from aqueous solution on two types of weakly basic polymeric sorbent, tertiary amine D301R and primary amine D392, was investigated over a wide pH range and at various salt (MgSO₄) concentrations. RESULTS: Overloading adsorption of pyruvic acid on both weakly basic polymeric sorbents occurred, with the overloading of D392 being greater than that of D301R. The adsorption of pyruvic acid on both sorbents was greatly affected by the solution pH and the salt concentration in the aqueous phase. An overloading model was able to predict the experimental uptake data very well. CONCLUSION: Solution pH is one of the most important operating conditions, and both polymeric sorbents D392 and D301R can be used to recover pyruvic acid from dilute aqueous solution with high efficiency at a solution pH around 2. The uptake by D392 is greater than that by D301R owing to steric hindrance of the tertiary amine. Copyright © 2008 Society of Chemical Industry     

Synthesis of p‐aminophenol from the hydrogenation of nitrobenzene over metal–solid acid bifunctional catalyst

BACKGROUND: A single‐step conversion of nitrobenzene (NB) to p‐aminophenol (PAP) through catalytic hydrogenation is a widely used synthesis route for PAP. The main shortcoming of this route is the use of sulfuric acid for rearrangement of the phenylhydroxylamine (PHA) intermediate. In this paper, S₂O₈^2?/ZrO₂ (PSZ) solid acid and Pt‐S₂O₈^2?/ZrO₂ (Pt‐PSZ) bifunctional catalysts were prepared for the synthesis of PAP in non‐acid medium. RESULTS: Calcination temperature has a substantial effect on the acidity, structure and activity for PHA rearrangement of PSZ. The highest PAP yield was 33.8% over PSZ calcined at 823 K when the reaction was carried out in water at 423 K. A high PAP yield of 23.9% was achieved by a single‐step reaction of nitrobenzene over Pt‐PSZ bifunctional catalysts. CONCLUSION: PSZ solid acid exhibits high activity for PHA rearrangement. Perfect tetragonal ZrO₂ and much stronger acid sites play important roles in catalytic activity. Inhibiting the hydrogenation activity by reducing the amount of Pt loading on Pt‐PSZ can improve the competition of PHA rearrangement on acid sites with hydrogenation of PHA on metal active sites, resulting in better selectivity to PAP. Copyright © 2008 Society of Chemical Industry     

Application of artificial neural networks to the analysis of two‐dimensional fluorescence spectra in recombinant E coli fermentation processes

A two‐dimensional (2D) spectrofluorometer was used to monitor various fermentation processes with recombinant E coli for the production of 5‐aminolevulinic acid (ALA). The whole fluorescence spectral data obtained during a process were analyzed using artificial neural networks, ie self‐organizing map (SOM) and feedforward backpropagation neural network (BPNN). The SOM‐based classification of the whole spectral data has made it possible to qualitatively associate some process parameters with the normalized weights and variances, and to select some useful combinations of excitation and emission wavelengths. Based on the classified fluorescence spectra a supervised BPNN algorithm was used to predict some of the process parameters. It was also shown that the BPNN models could elucidate some sections of the process's performance, eg forecasting the process's performance. Copyright © 2005 Society of Chemical Industry     

对我厂防治加热管内碳酸钙垢的思索

分析了我厂两碱法原卤净化后,加热管内壁结碳酸钙垢的原因,探讨了我厂采取加盐酸、加阻垢剂、用超声波阻垢器的方法,以及对加热管内碳酸钙垢防治的情况和存在的问题.     

Lactic acid production from dining‐hall food waste by Lactobacillus plantarum using response surface methodology

BACKGROUND: Food waste generally has a high starch content and is rich in nutritional compounds, including lipids and proteins. It therefore represents a potential renewable resource. In this study, dining‐hall food waste was used as a substrate for lactic acid production, and response surface methodology was employed to optimise the fermentation conditions. RESULTS: Lactic acid biosynthesis was significantly affected by the interaction of protease and temperature. Protease, temperature and CaCO₃ had significant linear effects on lactic acid production, while α‐amylase and yeast extract had insignificant effects. The optimal conditions were found to be an α‐amylase activity of 13.86 U g^?1 dried food waste, a protease activity of 2.12 U g^?1 dried food waste, a temperature of 29.31 °C and a CaCO₃ concentration of 62.67 g L^?1, which resulted in a maximum lactic acid concentration of 98.51 g L^?1 (88.75% yield). An increase in inoculum size would be appropriate for accelerating the depletion of initial soluble carbohydrate to enhance the efficiency of α‐amylase in dining‐hall food waste fermentation. CONCLUSION: A suitable regression model for lactic acid production was developed based on the experimental results. Dining‐hall food waste was found to be a good substrate for lactic acid fermentation with high product yield and without nutrient supplementation. Copyright © 2008 Society of Chemical Industry     

Dissolution kinetics of ulexite in acetic acid solutions

Ulexite is an important boron mineral used for the production of boron compounds. The aims of this study are to examine the dissolution kinetics of ulexite in acetic acid solutions, and to present an alternative process to produce boric acid. In order to investigate the dissolution kinetics of ulexite in acetic acid solutions, the concentration of solution, reaction temperature, solid-to-liquid ratio, and particle size were selected as experimental parameters. It was determined that the dissolution rate of ulexite increased with increasing solution concentration and temperature and decreasing particle size and solid-to-liquid ratio. The activation energy of the process was found to be 55.8 kJ/mol.     

Interfacial polycondensation of diphenolic acid and isophthaloyl chloride

Interfacial polycondensation of diphenolic acid (DPA) and isophthaloyl chloride (IPC) in various solvent/water systems was investigated with tetrabutyl ammonium chloride as a phase transfer catalyst. It was found that a large mass of capsules were formed at the beginning of the reaction for all solvents examined but the capsule morphology and reaction results depended on the solvents. It is believed that the capsule shells make up of the reaction zone and a mechanism of the interfacial polycondensation is proposed accordingly. The effect of the solvents on the reaction was interpreted from the interaction between the polymer and the solvent according to the mechanism. The reaction conditions were optimized, and poly(DPA-IPC) with high intrinsic viscosity was prepared in high yield under the optimal condition. It is an amorphous polymer with glass transition temperature of about 160°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Novel approach in investigation of the poly(acrylic acid) hydrogel swelling kinetics in water

The swelling kinetics curves of structurally defined poly(acrylic acid) hydrogel in bidistilled water at temperatures: 25, 30, 35, 40, and 45°C were determined. The possibility of kinetically explaining the isothermal swelling process by applying the following models: reaction controlled by diffusion, first order chemical reaction kinetics, and second order chemical reaction kinetics, was investigated. It was found that kinetically explaining the swelling process using these methods was limited to only certain parts of the process. The swelling process in bidistilled water was described in full range assuming that the hydrogel's swelling rate was a kinetically controlled reaction by the rate of the movement of reactive interface of hydrogel. Based on that model, the kinetic parameters, activation energy (E_a) and preexponential factor (A), of the swelling process were determined to be E_a = 35 kJ/mol and lnA = 8.6. A possible mechanism of the investigated swelling process was discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A strategy for the electro-organic synthesis of new hydrocaffeic acid derivatives

Electrochemical treatment processes can significantly contribute to the protection of the environment through the minimization of waste and toxic materials in effluents. From a pharmaceutical point of view and due to the existing resemblance between the electrochemical and biological reactions, it can be assumed that the oxidation mechanisms on the electrode and in the body share similar principles. In this paper, the application of electrochemical studies in the design of an environmentally friendly method was delineated for the new hydrocaffeic acid (HCA, 3,4-dihydroxy hydrocinnamic acid) derivatives synthesis at carbon electrodes in an undivided cell. In this cell, the EC mechanism reaction was involved, comprising two steps alternatively; (1) electrochemical oxidation and (2) chemical reaction. In particular, the electro-organic reactions of HCA, an important biological molecule, were studied in a water–acetonitrile (90:10 v/v) mixture in the presence of benzenesulfinic acid (3) and p-toluenesulfinic acid (4). The research included the use of a variety of experimental techniques, such as cyclic voltammetry, controlled-potential electrolysis and product spectroscopic identification.     

Effect of alkyl chain length on the electrochemical perfluorination of n-alkane (C6–C10) carboxylic acid chlorides

Electrochemical perfluorination (ECPF) of n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl and n-decanoyl chlorides was carried out under identical experimental conditions in liquid HF. The product distribution among perfluorinated carboxylic acids, perfluoro ethers, perfluoroalkanes, isomerised and fragmented products containing less number of carbon atoms was identified using ¹⁹F NMR. The selectivity of C₆–C₁₀ perfluoro carboxylic acid varied between 29 and 36%. The alkali insoluble perfluoro cyclic ether and perfluoro alkane fractions increased with increasing chain length. The increase of perfluoroalkane fractions is mainly due to decarboxylation. Cyclic ether fractions also decreased slightly with increase in chain length. Among the cyclic ethers α substituted oxolanes were the predominant products. Six membered cyclic ethers were always found to contain β substitution. The possible pathways for these products are also indicated. An erratum to this article can be found at