Decolorisation of crude palm oil by acid-activated spent bleaching earth

Regeneration of spent bleaching earth by acid activation and heat treatment has been investigated. Spent bleaching earth was activated by H₂SO₄ of various concentrations (1–40%) and heat treated at 120°C–350°C. The experimental results indicate that treatment of spent bleaching earth with 10% H₂SO₄ at 350°C produced a material which was most effective in removing coloured pigments from crude palm oil. Subsequent experiments were conducted using this particular acid-treated spent bleaching earth. Various parameters which affect the sorption process were studied. They include initial crude palm oil concentration, sorbent dosage and temperature. Applicability of both the Freundlich and Langmuir isotherms to the acid-treated spent bleaching earth–palm oil hexane miscella system indicates that both physiosorption and chemisorption were involved in the sorption process. Measurements of various quality parameters of bleached and crude palm oils were carried out. They include Lovibond Colour index, carotene content, peroxide value, free fatty acid, fatty acid composition and iodine value. The results show that the bleached palm oil retained good oil quality after the decolorisation process using 10% acid-treated spent bleaching earth with a Lovibond Colour of 6·4. © 1998 SCI     

Al-Pillared clay for cottonseed oil bleaching: An optimization study

In this study, Al-pillared white bentonite (Ordu-Unye, Turkey) was used for cottonseed oil bleaching. Pillaring process parameters were optimized in terms of bleaching efficiency as the bleaching capacity of cottonseed oil. The initial cation concentration, hydrolyzing agent ratio, and thermal treatment temperature were chosen as major process parameters. Pillared clays were characterized by FTIR and differential thermal analysis. The bleaching efficiency of bentonite increased from 11.8 to 17.5% by acid activation and to 33.5% by further Al pillaring. The optimal pillaring process conditions for cottonseed bleaching were an initial concentration of AICl₃, of 0.5 M, a OH⁻/Al³⁺ molar ratio of 0.3, and a thermal treatment temperature of 700°C.     

Influence of olive crushing methods on the yields and oil characteristics

In the last years, metallic crushers substituted granite stone mill with some variations in the organoleptic oil characteristics. To control the influence of the crushing method on the yield and oil quality, the olive pastes were obtained using three different ways: (i) new metallic crusher at mobile knives; (ii) granite stone mill; (iii) double olive crushing by the metallic crusher and the granite stone mill. With the aim to ascertain the useful use of a new metallic crusher (at mobile knives), experimental tests were carried out in an industrial oil mill. This oil mill is equipped by a centrifugal decanter generating two oil flows: first and second extraction (recovery) oils. The results showed that the yields obtained by different methods were satisfactory. No statistically significant differences have been observed in terms of oil yield and quality when different crushing devices were used. All first extracted oils are extra virgin with similar organoleptic characteristics, especially for the fruity intensity and for the bitter and pungent taste, as confirmed by the composition of volatile substances and the content of phenolic oil compounds. The recovery oils (second extraction oils) showed, in contrast to first extraction oils, a more intense green colour and a higher content of total phenols. Practical applications: Processing of sound olives with the right ripening grade and good quality allows to easily obtain an extra virgin olive oil, with commercial qualitative parameters according to the European Union requirements. However, different olive crushing systems affect the concentrations of some compounds responsible of aroma and taste (phenolic compounds). The use of the more violent metallic crushers facilitates obtaining oils with total phenol content higher than when using a stone mill. Here we used a particular metallic crusher (at knives) that, however, is suitable to replace the granite stone mill when a less pungent and bitter oil is required.     

Elimination of polycyclic aromatic hydrocarbons by bleaching of olive pomace oil

A detailed study of the efficacy of the bleaching process for elimination of polycyclic aromatic hydrocarbons in Spanish olive pomace oils has been carried out. For this purpose active carbon with bleaching earth was used as absorbent. The amount of benzo‐(α)‐pyrene was determined by reversed‐phase high‐performance liquid chromatography with a Fluorimetric detector. The use of exhausted filter‐cakes in countercurrent processes with a cake formed of active carbon and bleaching earth is very efficient for reducing the initial content of benzo‐(α)‐pyrene before the addition of fresh adsorbent, thus reducing the amounts of carbon and earth required.     

Solvent efficiency for oil extraction from spent bleaching clay

Various alcohols and hydrocarbons were used as solvents to extract the residual oil in spent bleaching clay from palm oil refining. The content of oil and minor components in the spent clay was >40% by weight. The efficiencies of extraction by the polar alcohols, except for methanol, were higher but with a slower initial rate than the nonpolar hydrocarbons. The free fatty acids contents, the Totox values (anisidine value+2 x peroxide value), and the color of the alcohol-extracted oil were also higher than that by the hydrocarbons resulting in poorer quality oils. All the extracted oils, irrespective of the solvent used, have poorer quality than crude palm oil. However, for regeneration of the residual spent clay, the polar alcohols should be more suitable as more of the impurities are removed.     

Influence of ecological cultivation on virgin olive oil quality

The quality of oil extracted from ecologically cultivated olives of the Picual variety was compared with oil extracted from Picual olives cultivated using conventional methods. Olive trees were grown in a two-section plot. Fruits from each plot were harvested at various stages of ripeness, and acidity value, peroxide index, ultraviolet absorption at 232 and 270 nm, stability to oxidation, sensory analysis, fatty composition, and contents of tocopherols, phenolic compounds, and sterols were determined on oil extracted from each treatment. The results showed that the organic virgin olive oil was of a superior quality to the conventional virgin olive oil in all the quality parameters analyzed.     

A laboratory study of the bleaching process in stigmasta-3,5-diene concentration in olive oils

The bleaching effect was simulated in pilot plant by measuring the influence of temperature (40, 50, 60, 70, 80, and 90°C), time (5, 10, 15, 20, 25, and 30 min), and concentration of solid adsorbent [1.5 and 8% (w/w) of Tonsil supreme NFF] on stigmasta-3,5-diene (STIG) obtained by dehydration of steroidal compounds. Conditions were chosen to simulate those used in industrial operations. The presence of refined oils in extra virgin olive oil can be detected by these newly formed steroid hydrocarbons. Experimental results indicated that STIG did not exceed an imposed limit of 0.15 mg/kg in extra virgin olive oil, when oils were bleached with 1.5% earth at temperatures ≤80°C for 30 min in admixed to oils sold as virgin. A large proportion of the adulterations were not detectable by the official methods. Color determinations (CIE-1931) chromatic coordinates) were replicated on a refined oil and in admixed extra virgin olive oil. Color of olive oil was not significantly affected by mixing with refined oil (≤20%).     

Evaluation of the bitter taste in virgin olive oil

An analytical method has been developed to evaluate the intensity of the bitter taste in virgin olive oil. Results from the proposed method, based on extraction of the bitter constituents of virgin olive oil with methanol/water and measurement of the absorbance at 225 nm, show a significant correlation with the intensity of bitterness that had been evaluated in a sensorial manner by a panel. The developed method, therefore, offers a real alternative to the panel test for the evaluation of this attribute.     

Influence of the extraction process on dissolved oxygen in olive oil

The influence of the olive oil processing steps [paste malaxation (PM), decanter centrifugation (DC), and vertical centrifugation (VC)] on the dissolved oxygen (DO) concentration in virgin olive oil (VOO) right after production was investigated at industrial plant scale for two successive years. The influence of this parameter on quality decay during shelf life, assessed by peroxide value (PV) analysis, was also monitored. The VC step showed the higher oxygenation effect (50% increase in comparison to the control), and a good linear regression (r² = 0.83) was found between the initial DO concentration and the PV after 2 days. An 18‐months shelf life test, performed on VOO sampled before and after the VC, indicated the slowest decay kinetics in the oils with the lower initial DO concentration, i.e. the non‐centrifuged oils.     

Adsorption of chlorophyll-a from acetone solution on natural and activated bentonite

The adsorption of chlorophyll-a on bentonite desiccated at 110°C, untreated and acid-treated with H₂SO₄ solutions over a concentration range between 0·25 and 2·50 mol dm^?3, from acetone solution at 25°C has been studied. The adsorption isotherms may be classified as using Giles' classification, as type S (untreated sample and 0·25 mol dm^?3 H₂SO₄-treated sample), type H (0·50 mol dm^?3 H₂SO₄-treated sample) and type L (1·00 and 2·50 mol dm^?3 H₂SO₄-treated samples). This fact suggests that the bentonite surfaces (low, high and medium affinity, respectively) behave in differently relation to the adsorption of the chlorophyll-a molecules. The experimental data points have been fitted to the Freundlich equation in order to calculate the adsorption capacities (K_f) of the samples; K_f values range from 0·43 mg kg^?1 for the untreated bentonite up to 108·89 mg kg^?1 for the 0·50 M H₂SO₄-treated bentonite. The removal efficiencies (R) have also been calculated and range from 5·71% for the untreated bentonite up to 85·18% for the 0·50 M H₂SO₄-treated bentonite.     

Use of nitrogen to improve stability of virgin olive oil during storage

Experiments were carried out to study the possibility of improving the stability of extra virgin olive oil by using nitrogen as a conditioner gas during storage. With this aim, virgin olive oil samples, obtained from Leccino and Coratina cultivars, were stored in the dark, in closed bottles conditioned with air or nitrogen at 12–20 and 40°C. Results indicated that the FFA percentage increased over 1% only when oils were stored at 40°C. The PV and the K ₂₃₂ value (light absorbance at 232 nm) of oils increased over the limit value allowed by European Union law when the bottles were only partly filled and air was the conditioner gas. The use of nitrogen as conditioner gas helped to avoid this risk during 24 mon of storage at 12–20°C. The total phenolic content of both cultivars oils decreased during storage because their oxidation protected the oils from autoxidation. The content of total volatile compounds in oils decreased continuously during storage at 12–20°C, whereas it increased over 10 (Coratina cv.) and 15 (Leccino cv.) mon and then diminished when the storage temperature was 40°C. The same behavior, i.e., increase then decrease, was ascertained for trans-2-hexenal. The hexanal content of oils increased continuously during storage because this compound is formed by the decomposition of the 13-hydroperoxide of linoleic acid.     

Toxic effect of coloured olive compounds on the anaerobic digestion of olive oil mill effluent in UASB-like reactors

Anaerobic sludge digestion of olive oil mill effluent (OOME) in Upflow Anaerobic Sludge Blanket (UASB) reactors was shown to be unstable as a result of both chemical and biological parameters. The study was complicated by the fact that Chemical Oxygen Demand (COD) was removed by growth and maintenance of active biomass and by adsorption in and on the sludge. Coloured compounds caused an inhibition effect on the anaerobic digestion of the wastewater. This inhibition, shown at low COD concentrations of diluted OOME, was due to accumulation of recalcitrant coloured compounds in the sludge, inducing irreversible inhibition of bacterial growth. Partial decolourization of OOME through resin (Duolite XAD 761) treatment reduced the toxic effect.     

Effect of extraction systems on the quality of virgin olive oil

Research has been carried out to ascertai the effects of different processing systems on olive oil quality. Tests were performed in industrial oil mills that were equipped with both pressure and centrifugation systems. Results show that oils extracted from good-quality olives do not differ in free fatty acids, peroxide value, ultraviolet absorption and organoleptic properties. Polyphenols ando-diphenols contents and induction times are higher in oils obtained from good-quality olives by the pressure system because it does not require addition of water to the olive paste. The centrifugation system requires the addition of warm water to the olive paste and helps to obtain oils with a lower content of natural antioxidants. Oils obtained from poorquality or from ripe olives in continuous centrifugal plants are lower in free fatty acids than those obtained by the pressure system. Dr. Mario Solinas is deceased—May 23, 1993.     

De-oiling contaminated bleaching clay by high-pressure extraction

The disposal and re-use of spent bleaching clay from the vegetable oil processing industry is a problem of growing importance. Although today the only practical way of removal of the spent material is disposal, extraction with organic solvents is a well-known method of de-oiling contaminated bleaching clay. In our investigations we compare the extractibility of two different types of bleaching clays with CO₂ as a solvent. All experiments were carried out with a high-pressure extraction plant. The extraction and separation conditions, temperature and pressure, as well as the CO₂ mass flow, were varied during experiments. The aim of our investigations was a complete separation of the oil from the adsorbent. The latter should then be re-used as bleaching clay. The oil and the bleaching clay were analyzed and tested, respectively. The results show that oil of good quality can be recovered and the bleaching clay still has an activity approximately 50% of fresh clay.     

Preparation of activated carbon from olive mill solid residue

A process was developed for producing high quality activated carbon from Algerian mill waste. The solid olive mill residue was carbonized at 800 °C and physically activated with CO₂, air or steam. An optimum activation temperature of about 850 °C was determined for all the activation agents used. Steam appeared to be the most efficient activator as compared with air and CO₂. An optimal activation time of about 2 h was then determined with steam as the optimum activation agent. The porous structure of the activated carbon was characterized by nitrogen adsorption at −196 °C, and in all cases the surface areas, calculated by DR and BET methods, confirmed the production of a material with good microstructural characteristics and specific surfaces exceeding 1500 m² g⁻¹ for the carbon prepared by steam activation. Phenol adsorption isotherms gave the adsorption properties and the adsorption capacity of about 11.24 mg of phenol per gram of the activated carbon produced. The kinetics of the phenol adsorption onto the porous material was evaluated by means of two models: the external resistance model and the linear model. The second model appeared to constitute a more appropriate fit for the experimental data. © 2000 Society of Chemical Industry     

Adsorption isotherms in bleaching hazelnut oil

Adsorption isotherms in bleaching hazelnut oil were determined to investigate the applicability of the Langmuir and Freundlich equations and to elucidate the adsorption characteristics of oil on bentonite EY-09 (Bensan Co. Ltd., Edirne, Turkey). The degree of bleaching was monitored spectrophotometrically. Absorbance measurements were carried out to investigate the adsorption force of clay during bleaching of hazelnut oil with 0.3, 0.5, 0.7, and 0.9 wt% clay at 50, 60, 70, 80, and 90°C. Bentonite EY-09 was used as the bleaching clay (adsorbent). Plots of log(x/m) vs. log X _e (for the Freundlich isotherm) and X _e /(x/m) vs. X _e (for the Langmuir isomtherm) were made (where x is the amount of pigment removed per unit mass of the adsorbent, m, and X _e is the equilibrium concentration of the pigment). The Freundlich constants were found to increase with temperature for a given oil/bleaching agent ratio, showing the formation of more active sites on the adsorbent with a rise in temperature. Since the heat evolved during adsorption (0.32–1.03 kJ mol⁻¹) was less than 20 kJ mol⁻¹, the forces between the adsorbent and adsorbate appeared to be van der Waals forces. This type of adsorption is defined as physical or van der Waals adsorption. The results obtained show good agreement with the Freundlich isotherm, indicating that the adsorption of the pigment from the oil proceeds by monolayer formation on the surface of the adsorbent.     

Colza oil bleaching through optimized acid activation of bentonite. A comparative study

The acid activation of an Algerian bentonite was investigated using a factorial 3³ experiment design in order to improve the bleaching capacity in the colza oil processing. Optimized acid treatment of this bentonite gave rise to an effective bleaching earth in colza oil treatment. The 80 °C temperature value was regarded as being convenient in this study. For this purpose, the effects at 80 °C of three key parameters were investigated, namely the effects of the acid concentration in aqueous solution, the contact time and the clay to acid (S/L) ratio upon the clay effectiveness, regarded as the response function to be prone to modeling, simulation and optimization. The results showed that the acid concentration displays a stronger individual effect, as compared to the other parameters. In optimal activation conditions (acid concentration 31%, contact time 10 h and solid to liquid ratio 320 g/L), the highest bleaching capacity was found to be 99%. Comparison of the bleaching capacity from our bentonite shows that similar performances require less acid activated bentonite than any other bentonite. The acid acid-activated bentonite displayed also even higher color and chlorophyll removal than both the Tonsil and Maghnia standards, for similar bleaching earth amounts. The recommended features for the colza oil were obtained using only 1 wt.% of acid-activated bentonite, as compared to the Tonsil and Maghnia standard (1.2–1.4 and 2 wt.%, respectively). The model adequacy was also verified through additional bleaching experiment within the fixed parameters ranges, and was discussed.     

Detection of pressed hazelnut oil in admixtures with virgin olive oil by analysis of polar components

Analysis of the polar fraction from virgin olive oil and pressed hazelnut oil by high-performance liquid chromatography showed marked differences in the chromatograms of the polar components in the two oils. Six commercial samples of pressed hazelnut oil and 12 samples of virgin olive oil (or blended olive oil including virgin olive oil) were analyzed. The phenolic content of the pressed hazelnut oil samples was 161±6 mg·kg⁻¹. Inspection of the chromatograms showed that the pressed hazelnut oil extracts contained a component that eluted in a region of the chromatogram that was clear in the olive oil samples, and consequently this component could be used to detect adulteration of virgin olive oil by pressed hazelnut oil. The component had a relative retention time of 0.9 relative to 4-hydroxybenzoic acid added to the oil as an internal standard. The ultraviolet spectrum of the component showed a maximum at 293.8 nm, but the component could not be identified. Analysis of blends of oils showed that adulteration of virgin olive oil by commercial pressed hazelnut oil could be detected at a level of about 2.5%.