Enzymatic production of alkyl esters through alcoholysis: A critical evaluation of lipases and alcohols

This paper focuses on a detailed evaluation of commercially available immobilized lipases and simple monohydric alcohols for the production of alkyl esters from sunflower oil by enzymatic alcoholysis. Six lipases were tested with seven alcohols, including straight and branched-chain primary and secondary alcohols. The reactions were conducted in a batch stirred reaction vessel using stoichiometric amounts of substrates under solvent-free conditions. Dramatic differences in alcoholysis performance were observed among the different lipases. For most of the alcohols, Novozym 435 produced the highest yield of FA alkyl esters, with yields well over 90% for methanol, absolute ethanol, and 1-propanol. Overall, 96% ethanol was the preferred alcohol for all lipases except Novozym 435, and ethanolysis reactions reached the maximal conversion efficiency. Increasing the water content in the system resulted in an increased degree of conversion for all lipases except Novozym 435. The secondary alcohol 2-propanol significantly reduced the alcoholysis reaction with all lipases; however, the branch-chain isobutanol was more advantageous than linear 1-butanol for Novozym 435, Lipozyme RMIM, and Lipase PS-C. Many commercial immobilized lipases are highly efficient and promising for the production of alkyl esters, offering high reaction yields and a simple operation process.     

Removal of phosphate from wastewaters

Gas concrete waste was used to remove phosphate from aqueous solutions in this study. The influence of suspension pH, temperature, mixing rate, and gas concrete dosage on phosphate removal was investigated by conducting a series of batch adsorption experiments. In addition, the yield and mechanisms of phosphate removal were explained on the basis of the results of X-ray spectroscopy, measurements of zeta potential of particles, both values of BET-N₂ specific surface area, and images of scanning electron microscopy (SEM) of the particles before and after adsorption. In this study, phosphate removal in excess of 99% was obtained and it was concluded that wastes of gas concrete are an efficient adsorbent for the removal of phosphate. The removal of phosphate predominantly takes place by precipitation mechanism and the weak physical interactions between the surface of adsorbent and the metallic salts of phosphate.     

Graft Copolymerization of Acrylamide onto Oil Palm Empty Fruit Bunch (OPEFB) Fiber

Grafting of acrylamide (AAm) onto oil palm empty fruits bunch fiber using hydrogen peroxide as initiator and methyl acrylate as comonomer was investigated. The amount of comonomer needed to make grafting of acrylamide possible was determined. The percentage of poly(acrylamide) and the comonomer in the final graft copolymer was estimated by elemental analysis. Results obtained indicated that methyl acrylate facilitated the incorporation of acrylamide monomer onto OPEFB. The reactivity ratios for both monomers were determined by using Fineman–Ross plot. The effects of reaction temperature and period as well as amount of the initiator, solvent, monomer and comonomer on the percentage of grafting at fixed amount of comonomer (11 mmol) were studied. Maximum percentage of grafting was achieved when the amount of initiator and solvent 3.98×10⁻³ mol and 50 mL respectively. The optimum reaction temperature was 50 ^○C and the reaction period was 90 min. Highest percentage of grafting was 232% when 25.6 mmol of acrylamide was used under these optimum conditions. The presence of functional group in the grafted polymer is characterized by infrared spectroscopy and the surface morphology is observed by scanning electron microscopy. Thermoanalytic investigation on OPEFB and OPEFB-g-PAAM were carried out to evaluate the thermal stability and respective activation energy of the materials.     

The pseudo-single-phase,base-catalyzed transmethylation of soybean oil

The base-catalyzed transmethylation of soybean oil has been studied under conditions whereby the reaction starts as a single phase, but later becomes two phases as glycerol separates. Methanol/oil molar ratios of 6∶1 were used at 23°C. The catalysts were sodium hydroxide (0.5, 1.0, and 2.0 wt%), potassium hydroxide (1.0 and 1.4 wt%), and sodium methoxide (0.5, 1.0, and 1.35 wt%), all concentrations being with respect to the oil. Oxolane (tetrahydrofuran) was used to form a single reaction phase. The reactions deviated from homogeneous kinetics as glycerol separated, taking with it most of the catalyst. When 1.0 wt% sodium hydroxide was used, the methyl ester content reached 97.5 wt% after 4 h, compared with 85–90 wt% in the two-phase reaction. Sodium hydroxide (1.0 wt%), sodium methoxide (1.35 wt%), and potassium hydroxide (1.4 wt%) gave similar results, presumably because the same number of moles was used. The ASTM biodiesel specification for chemically bound glycerol was achieved after only 3 min when 2.0 wt% sodium hydroxide was used. However, the standard was not achieved after 4 h when 1.0 wt% sodium hydroxide was used, the MG content being 1.1–1.6 wt%. The use of 2.0 wt% catalyst is commercially impractical.     

A kinetic model for polystyrene (PS) pyrolysis reaction

A mathematical model for the pyrolysis reaction of polystyrene (PS) in a semi-batch reactor has been presented. The thermal degradation of PS was flexibly modeled by a combination of random and specific chain-end scissions. Numerical simulation was used to investigate the effect of operating conditions on the PS products spectrum, the results of which were validated by the experimental data. It was found that as the reaction temperature increased (decreased), the monomer fraction in the products became lower (higher) while the trimer higher (lower). No significant variation in the product composition was, however, observed while constant temperature was maintained. These results indicate the reaction temperature is an effective manipulated variable for the control of products composition of PS pyrolysis. The calculation of the optimum temperature trajectories through the optimization study can thus be of interest for achieving productivity enhancement in plastics pyrolysis processes. This paper is dedicated to Professor Dong Sup Doh on the occasion of his retirement from Korea University.     

Study of the amination of fatty alcohols catalyzed by Cu−Ni catalysts

Amination of fatty alcohols by hydrogenation and dehydrogenation catalysis is one of the main commercial processes for the production of dimethylalkylamines. The key factor in this process is the preparation of catalysts with high selectivity. A study of amination catalyzed by Cu−Ni catalysts supported on CaCO₃ is reported in this paper. Selectivity of the catalysts was adjustable by varying the ratio of Cu to Ni or by adding a third element (Zn or Mg). The promotion of catalyst selectivity was mainly attributable to the effect of the components on the reducibility of Ni²⁺ in the catalysts. Lower reducibility of Ni²⁻ led to higher catalyst selectivity.     

Release rates of tetradecen-1-ol acetates from polymeric formulations in relation to temperature and air velocity

An apparatus was developed for investigating the release rates of pheromone formulations at temperatures and air velocities that correspond with those in the field. Polyurethane foam proved an excellent adsorbent for the recovery of tetradecen-1-ol acetates, allowing high air flows at low differential pressure and without breakthrough of these compounds. The experimental setup and procedures are described. The release rates of all formulations investigated were almost proportional to the square root of air velocity, and their logarithms were proportional to the reciprocal of temperature (K). When temperature is increased from 15°C to 25°C, the release rates increase by about 2-2.5 ×. Both relationships were combined into one equation that allows a reliable estimate to be made of the actual release rates of a formulation, under varying conditions, on the basis of its specific parameters and the relevant meteorological data.     

Drawing non‐layered tidy trees in linear time

The well‐known Reingold–Tilford algorithm produces tidy‐layered drawings of trees: drawings where all nodes at the same depth are vertically aligned. However, when nodes have varying heights, layered drawing may use more vertical space than necessary. A non‐layered drawing of a tree places children at a fixed distance from the parent, thereby giving a more vertically compact drawing. Moreover, non‐layered drawings can also be used to draw trees where the vertical position of each node is given, by adding dummy nodes. In this paper, we present the first linear‐time algorithm for producing non‐layered drawings. Our algorithm is a modification of the Reingold–Tilford algorithm, but the original complexity proof of the Reingold–Tilford algorithm uses an invariant that does not hold for the non‐layered case. We give an alternative proof of the algorithm and its extension to non‐layered drawings. To improve drawings of trees of unbounded degree, extensions to the Reingold–Tilford algorithm have been proposed. These extensions also work in the non‐layered case, but we show that they then cause a O(n²) run‐time. We then propose a modification to these extensions that restores the O(n) run‐time. Copyright © 2013 John Wiley & Sons, Ltd.     

Process development for the removal of copper from wastewater using ferric/limestone treatment

The removal of copper from wastewater by ferric/limestone coagulation followed by screen filtration was carried out at a laboratory scale. The optimum coagulant (FeCl₃) dose and working pH were 50 mg// of Fe(m) and pH 7.5, respectively, through jar tests. For the efficient removal of copper from wastewater, we developed a novel process including the co-precipitation of copper with FeCl₃, alkalization in a limestone aeration bed, and separation of precipitates in a sedimentation tank coupled with internal stainless steel screen filter. The performance results showed that removal of copper from the solution was over 99.5%. The pH was effectively maintained over 7.5 in limestone bed during the whole process. Ferric hydroxide/copper aggregates were removed over 99% by stainless steel screen filter of 1,450 mesh. Periodic air backwashing alleviated fouling of the filter surface.     

Ionic liquids as electrolytes

Salts having a low melting point are liquid at room temperature, or even below, and form a new class of liquids usually called room temperature ionic liquids (RTIL). Information about RTILs can be found in the literature with such key words as: room temperature molten salt, low-temperature molten salt, ambient-temperature molten salt, liquid organic salt or simply ionic liquid. Their physicochemical properties are the same as high temperature ionic liquids, but the practical aspects of their maintenance or handling are different enough to merit a distinction. The class of ionic liquids, based on tetraalkylammonium cation and chloroaluminate anion, has been extensively studied since late 1970s of the XX century, following the works of Osteryoung. Systematic research on the application of chloroaluminate ionic liquids as solvents was performed in 1980s. However, ionic liquids based on aluminium halides are moisture sensitive. During the last decade an increasing number of new ionic liquids have been prepared and used as solvents. The general aim of this paper was to review the physical and chemical properties of RTILs from the point of view of their possible application as electrolytes in electrochemical processes and devices. The following points are discussed: melting and freezing, conductivity, viscosity, temperature dependence of conductivity, transport and transference numbers, electrochemical stability, possible application in aluminium electroplating, lithium batteries and in electrochemical capacitors.