SUBCRITICAL WATER EXTRACTION OF CAFFEINE FROM BLACK TEA LEAF OF IRAN

ABSTRACT

This study examines subcritical water extraction (SCWE) of caffeine from black tea leaf. The effects of various operating conditions such as water temperature (100, 125, 150 and 175C), water flow rate (1, 2 and 4 g/min), mean particle size (0.5, 1 and 2 mm) on extraction yield and rate were determined. SCWE at 175C, water flow rate of 2 g/min and mean particle size of 0.5 mm were found to be able to recover 3.82% (w/w) of caffeine present in the black tea leaf within 3 h of extraction. In comparison to the SCWE, conventional hot water extraction showed 3.30% (w/w) extraction yield. It was found also that pressure had no effect on extraction yield and rate.

PRACTICAL APPLICATIONS

Recently, subcritical water has become of great interest as an alternative solvent for extraction of natural active compounds. Subcritical water, as a green solvent, can be used in many different fields of applications. In recent years, extraction of flavors, fragrances and antioxidant components from plant materials, and hydrolysis of carbohydrates, vegetable oils and fatty acids have been widely investigated by many researchers. Using subcritical water for analytical purposes, for soil remediation and applying it as a reaction media are some other interesting fields for practical applications. Subcritical water is an excellent solvent for caffeine as well as many other organic compounds but is safer than the organic solvents that are used for caffeine extraction.     

REVIEW OF REVERSE OSMOSIS MEMBRANES AND TRANSPORT MODELS

After a brief introduction to membrane processes in general, and the reverse osmosis process in particular, the structure and properties of membranes and membrane transport theory are described. The mechanism of salt rejection and transport properties of membranes are discussed in detail. Solubility, diffusivity, and permeability of membranes to solutes and solvents are reviewed critically and compared with each other. Special attention is given to two particular types of membranes, cellulose acetate (CA) and aromatic polyamide (AP) membranes, which are often used for water desalination.

The major portion of this article is devoted to the review and discussion of membrane transport theory with application to the reverse osmosis and ultrafiltralion processes. It is shown that the solvent flux can be represented reasonably well by linear models such as the solution-diffusion model (Lonsdale, et al., 1965). The contribution of pore flow to the solvent flux is small. The solute flux, however, is not linearly dependent on the driving forces and one has to solve the differential equation of transport within the membrane which results in models such as the Spiegler-Kedem (1966) or the finely-porous (Merten, 1966) models. When the wall Peclet number is small, Pe_w =uτδ/D_sw ?1, (D_sw = bD_e one can linearize the nonlinear models. This requirement is not satisfied in most practical cases. Furthermore, the pore flow has significant effect on the solute flux equation and thus it can not be neglected.

The ambiguities that exist in the literature concerning the types of fluxes are discussed. The fluxes used in models derived from irreversible thermodynamics are purely diffusive (concentration and pressure diffusion) and they do not contain any convective effects; whereas the experimentally observed fluxes are the total fluxes with respect to the membrane which consist of a diffusive flux and a convective flux. A new model, based on irreversible thermodynamics, is derived which includes a convective term.

A membrane model is especially useful when the transport coefficients which define the model are not functions of the driving forces, i.e., pressure and concentration gradients. The coefficients in the solution diffusion and sotution-diffusion-imperfection (Sherwood, et al., 1967) models are functions of both pressure and concentration, while the coefficients in the Kedem-Katchalsky (1958) model are relatively insensitive to pressure and concentration. The nonlinear model of Spiegler-Kedem (1966) further improves the Kedem-Katchalsky model.     

The effect of circular bridge piers with different inclination angles toward downstream on scour

A fundamental principle in the safe design of bridge piers is to estimate maximum scour depth. As such, many researchers devoted their efforts to study the phenomenon of scour around bridge piers and to present relationships to estimate maximum scour depth. In the current research, scour around circular bridge piers with two different diameters and different inclination angles toward downstream has been investigated experimentally under clear water and different discharges. The obtained results revealed that increase in the inclination angle leads to a significant decrease in the scour depth, dimensions of sediment ridge and scour hole. Moreover, by comparing the data obtained from vertical bridge pier and well-known relationships, a relationship having the most agreement with the results was selected and modified to estimate equilibrium scour depth around inclined piers.     

Synthesis and properties of new polyimide/clay nanocomposite films

A series of polymer–clay nanocomposite (PCN) materials consisting of polyimide and typical clay were prepared by solution dispersion. Quaternary alkylammonium modified montmorillonite, Cloisite 20A, was used as organoclay. Poly(amic acid) solution was prepared from the reaction of benzophenone-4,4′,3,3′-tetracarboxylic dianhydride and 2-(5-(3,5-diaminophenyl)-1,3,4-oxadiazole-2-yl) pyridine in dimethylacetamide. Thermal imidization was performed on poly(amic acid)/organoclay dispersion in a regular temperature-programmed circulation oven. The study of interlayer d-spacing with X-ray diffraction pattern indicates that an exfoliated structure may be present in the nanocomposite 1%. Intercalated structures were obtained at higher organoclay loadings. Nanocomposites were studied using thermogravimertic analysis and differential scanning calorimetry. Nanocomposites exhibit higher glass transition temperature and improved thermal properties compared to neat polyimide due to the interaction between polymer matrix and organoclay particles. The results are also compared with data of a similar work. Morphology study with scanning electron microscopy showed that the surface roughness in nanocomposite 1% increased with respect to pristine polyimide. Solvent uptake measurements were also carried out for the prepared materials. Maximum solvent adsorption was observed for dimethyl sulfoxide (DMSO). It was found that the solvent uptake capacity decreased with increasing clay content.     

Nanohydroxyapatite synthesis using optimized process parameters for load-bearing implant

In this study, nanohydroxyapatite (NHA) was synthesized using calcium nitrate tetrahydrate and diammonium hydrogen phosphate via the precipitation method assisted with ultrasonication. Three independent process parameters: temperature (T) (70, 80 and 90°C), ultrasonication time (t) (20, 25 and 30 min), and amplitude (A) (60, 65 and 70%) were studied and optimized using response surface methodology based on 3 factors and 5 level central composite design. The responses of the model were analysed with the help of the particle size measured from field-emission scanning electron microscopy and Brunauer–Emmett–Teller (BET). The surface area of particle was measured with BET and the thermal stability of the powder was measured using thermogravimetric analysis. Finally, with the optimized process parameters obtained from the model, the NHA powder was synthesised and validated against the predicted value. The results show a good agreement with an average error 8% between the actual and predicted values. Moreover, the thermal stability and porosity of synthesized NHA was further improved after calcination. This improvement could be due to the removal of impurities from the NHA powder after calcination as indicated by the Fourier transform infrared spectroscopy and energy-dispersive X-ray spectroscopy.     

Effect of chemical composition and alumina content on structure and properties of ceramic insulators

In the present work, six electrical porcelain compositions with different amount of alumina and silica have been prepared and fired in an industrial furnace at 1300 °C. Density, porosity, bending strength and electrical strength were measured in the samples. In order to find a relationship between properties and sample microstructures, samples were analyzed by scanning electron microscope (SEM) and x-ray diffraction (XRD) techniques. The results showed that, with chemical composition of 53·5 wt.% SiO₂ and 37·5 wt.% alumina, highest electrical strength of 21·97 kV/mm was achieved in fabricated electrical porcelains. Increasing amount of alumina up to 30 wt.% decreases quartz and cristobalite phases, but increases corundum phase 3 to 5 times. SEM observation revealed that dense particles and uniform distribution of long and thin needle shaped mullite are predominant in sample microstructures with highest electrical strength.     

Stability of a Hurwitz polynomial under coefficient perturbations: necessary and sufficient conditions

Necessary and sufficient conditions for a perturbed polynomial to remain Hurwitz are given. The conditions allow considerable freedom in allocating different weights to various coefficients to reflect different levels of uncertainty in the coefficients. The new conditions are an extension of a previous result of the author in which sufficient conditions for the same problem were obtained.     

Determination of chloride, nitrate and calcium ions in sugar with ion selective-electrodes

Chloride, nitrate, and calcium ion-selective electrodes were tested and found satisfactory for the determination of the corresponding ions in highly refined white sugar, molasses and other impure sugar samples at different stages of sugar manufacturing or refining. The interferences by Br⁻ and I⁻ ions in Cl⁻ determination were eliminated by oxidation with 3 M HNO₃ and passing air to remove the free Br₂ and I₂ formed. The Cl⁻ concentration was then determined with a chloride-selective electrode against a calibration curve. Chloride should not be determined by ashing sugar, since this causes high losses of Cl⁻. It was found that NO₃⁻ and free Ca²⁺ ions could be determined directly in the sugar solution against corresponding calibration curves. Total calcium was determined after ashing of sugar samples. The ash was dissolved in 0.1 M HCl and passed through an anion exchange resin to remove PO³⁻₄ and SiO₂₋₃ ions, and Ca²⁺ was determined as before. Bound calcium was obtained by subtracting values of free from total calcium. Determination of bound calcium was useful to monitor the process of liming. For comparison, the three ions were also determined with acceptable precision without removing interfering ions using the method of standard addition and Gran's plot. The errors of determination for both direct and standard addition techniques were 3% for Cl⁻ and NO⁻₃ and 1–5% for Ca²⁺.