Determination of Metastable Zone Width and Nucleation Induction Period of Palm Oil and its Olein/Stearin in Melting Layer Crystallization

Measurement methods of metastable zone width (MZW) and nucleation induction time for melting layer crystallization of palm oil (PO) and its olein/stearin (POL/PST) were established, and the effects of cooling rate (corresponding to various supercoolings) on MZWs and induction time for melting layer crystallization of PO, POL, and PST were determined. The results indicated that the MZW coherently rose with increasing cooling rates with respect to PO and POL, while it declined with higher cooling rates for PST. The induction period results demonstrated that the nucleation induction periods of PO, PST, and POL decreased with increasing supercoolings, and the lag time for nucleation negatively correlated to the melting point of oils at the same supercooling. These data could offer significant instruction in designing and controlling the melting layer crystallization process for palm oil.     

Tripalmitin-Driven Crystallization of Palm Oil: The Role of Shear and Dispersed Particles

While palm oil (PO) is a reliable ingredient in formulations for biscuits, cream fillings, and compound chocolates, our understanding of its crystallization behavior and physico-chemistry pales in comparison to many other fats and oils. Phase diagrams of triacylglycerol (TAG) mixtures may be used to elucidate fat crystal polymorphism and composition of such oils, yet conditions important to the food industry such as shear speed, relevant processing temperatures, and presence of secondary ingredients are regularly overlooked. Here, the effects of shear speed (n = 0–500 RPM), dispersion concentration (0–5 wt.%), and dispersed particle surface chemistry [silica or octadecyl-functionalized (C18) silica] on the thermal properties of commercial PO when cooled from 60 to 20 °C at 1 °C min⁻¹ were explored, with focus placed on PO's higher-melting fraction. Using a series of high-purity TAG standards, X-ray diffraction revealed PO's higher-melting fraction as mainly composed of tripalmitin (PPP) crystals and molecular compounds (MC) of PPP either with 1,3-dipalmitoyl-2-oleoyl-sn-glycerol (POP) or with POP and 1,2-dipalmitoyl-3-oleoyl-rac-glycerol (PPO) in combination, all in a double chain-length β' (i.e., β'-2) conformation. Shear increased the formation of lower-melting α-2 POP and β'-2 MC_POP:PPO:PPP crystals while depleting the system of β'-2 MC_POP:PPP and β'-2 PPP crystals. This loss was further exacerbated by the addition of dispersed particles to the point where PPP was completely incorporated as MC and β'-2 PPP crystals were eliminated. While heterogeneous nucleation tends to favor kinetic products of fat crystallization, the interactions between shear and surface chemistry varied between crystal types.     

Effects of Ultrasonic Parameters on the Crystallization Behavior of Palm Oil

The crystallization behavior of palm oil (PO) without and with the application of high-intensity ultrasound (HIU) was investigated as the function of irradiation time (20, 60, 120, and 240 s), ultrasonic intensity (47.5, 95, 270, and 475 W) and temperature (20, 25, 30, and 36 °C). The effects on the crystallization behavior of PO were evaluated by ultraviolet/visible spectrophotometry, pulsed nuclear magnetic resonance and polarized light microscopy. Results indicated that all these parameters affected crystallization behavior. HIU significantly reduced the induction time and accelerated the crystallization rate at operating temperatures above 25 °C, but there was no significant difference at 20 °C due to high supercooling. The effects of HIU were more significant at higher power level and longer irradiation time, however, the thermal effect of ultrasound also increased with longer sonication time. The optimal sonication time was approximately 120 s which accelerated the crystallization rate of PO the most. The morphology studies suggested that HIU changed the growth mechanisms of crystals and generated smaller and uniformly crystals. At 36 °C, with extremely low supercooling condition, a combined effect was observed that prevented the separation of solid phase and liquid phase of the crystallized sample, and then led to a uniform distribution of crystals.     

Application of Ultrasound for Oil Separation and Recovery of Palm Oil

This work investigated whether ultrasound treatment could improve the oil recovery from the extract obtained from pressed oil palm mesocarp. Oil recoverable after subjecting two process streams from palm oil milling operations to ultrasound were compared to that obtained from corresponding samples without ultrasound treatment. The process streams examined were (i) the ex-screw press feed into the vertical clarification tank and (ii) the underflow sludge from the clarification tank. Oil recoverable was taken as the sum of decantable oil obtained after a gravity settling process at 85 °C for 1 h (skimmed oil) and oil released from the remaining colloidal dispersion after centrifugation at 1,000 g (centrifuged oil). Oil recoverable was dependent on the ultrasound treatment applied, type of transducer used and the feed stream. Increased recoverable oil was obtained by applying low frequency ultrasound (20 kHz) to the ex-screw press feed using a long rod radial sonotrode system but recoverable oil was decreased when a short single step cascade focused sonotrode system was used. High frequency ultrasound (400 + 1,600 kHz) increased recoverable oil from both process streams. Applying sequential low and high frequency ultrasound increased recoverable oil from the ex-screw press feed but decreased that from the underflow sludge. The use of high frequency ultrasound for improving oil recovery is a significant advance for palm oil milling operations.     

Kinetics of Palm Oil Methanolysis

A kinetics study of palm oil methanolysis was conducted at three different temperatures and three different concentrations of catalyst, sodium hydroxide, keeping constant the molar ratio of methanol to oil and the rotational speed of the impeller (6:1 and 400 rpm). The maximum conversion of palm oil and productivity to methyl esters were obtained at 60 °C and 1 wt% of NaOH based on palm oil, and they were 100 and 97.6%, respectively. The statistical analysis of conversions of palm oil and productivities to methyl esters as functions of temperature and concentration of catalyst, after 80 min of reaction, allowed them to fit second order polynomial equations, which adequately describe the experimental behavior. The experimental data appear to be a good fit into a second order kinetic model for the three stepwise reactions, and the reaction rate constants and the activation energies were determined. In this article we present the kinetic constant and activation energies for the experiments with 0.2% wt of NaOH. The effect of molar ratio on the concentration of products was investigated, while the temperature (55 °C), the concentration of catalyst (0.60 wt% of NaOH), and the rotational speed (400 rpm), were held constant. The results showed that the conversion and the productivity increased due to methanol excess, and were higher for the reactions with a molar ratio of 6:1.     

Effect of Milk Fat Concentration on Fat Crystallization of Palm Oil-Based Shortenings

The effect of different dosages of anhydrous milk fat (AMF) (25%, 50% and 75%, w/w) on shear-crystallization of fat blends made of refined palm oil, refined palm stearin, and rapeseed oil was studied. Classical techniques as differential scanning calorimetry (DSC), pulsed field gradient nuclear magnetic resonance (pfg-NMR), rheometer, and X-ray diffraction (XRD) were applied to evaluate the crystallization kinetics of fat blends as well as the fat compatibility between components in rapid cooling (15 °C min⁻¹), isothermal crystallization (at 15 °C), and storage (5 °C). Obtained results revealed that the mixtures of palm oils and milk fat had a low compatibility. The co-crystallization between triacylglycerols (TAG) of milk fat and of palm oil occurred during isothermal crystallization and storage resulting in slower crystallization kinetics and the formation of some eutectic mixtures.     

Physicochemical and Rheological Properties of Crystallized Blends Containing <Emphasis Type="Italic">trans</Emphasis>-free and Partially Hydrogenated Soybean Oil

Three vegetable oil blends, intended for formulation of high melting temperature confectionary coatings, were prepared by mixing different proportions of coconut oil, palm stearin, and either partially hydrogenated soybean oil (PH-SBO) or native soybean oil (i.e., trans-free SBO). The blends were crystallized under the same isothermal conditions and the crystallized systems evaluated by DSC, SFC, polarized light microscopy, and rheology under low [i.e., G′ and yield stress (σ*)] and high (i.e., creep and recovery profiles) stress forces. Overall, all trans-free blends showed lower SFC and heat of crystallization than the ones obtained with PH-SBO blends. These results showed that trans-fatty acids decrease the level of structural order of the crystals, and probably also the organization of the crystal network. As a result, most of the crystallized blends with PH-SBO showed lower σ* values and higher creep profiles (i.e., softer texture) than trans-free blends, particularly in systems crystallized at high supercooling and blends with saturated medium chain TAG. Nevertheless, at particular crystallization temperatures some trans-free formulations provided crystallized systems with rheological properties that would result in softer textures than the ones obtained with PH-SBO blends. Knowledge of the rheological properties under low and high stress forces is vital when comparing the functionality of crystallized TAG systems with and without TAG with trans-fatty acids.     

Rheological behavior of crystallizing palm oil

The static isothermal crystallization of palm oil was studied by oscillatory rheology. The phase angle, complex modulus, storage modulus and loss modulus were followed as a function of the crystallization time. Various crystallization temperatures were applied, and the results obtained by oscillatory rheology were compared with crystallization data obtained by more classical techniques like differential scanning calorimetry (DSC) and pulsed nuclear magnetic resonance (pNMR). It was shown that oscillatory rheology is a valuable complementary method to DSC and pNMR to evaluate primary crystallization. Like DSC and pNMR, oscillatory rheology is capable of differentiating whether crystallization occurs in a two‐stage or a single‐stage process. In addition, oscillatory measurements also allow the evaluation of aggregation, network formation and post‐hardening events like sintering and thus provide information on the crystal network and the final macroscopic properties of the crystallized sample.     

Fats from Chemically Interesterified High-Oleic Sunflower Oil and Fully Hydrogenated Palm Oil

Chemical interesterification of different lipid materials has considerable potential for the production of a wide variety of special fats with improved functional and nutritional properties. The present study aimed to evaluate the chemical interesterification of blends of high-oleic sunflower oil (HOSO) and fully hydrogenated palm oil (FHPO) in the ratios (% w/w) of 80:20, 70:30, 60:40 and 50:50. The blends were characterized in triacylglycerol composition, melting point, solid fat content and crystallization behavior, and some applications in food products were suggested. The interesterification altered the solid fat content, melting point and crystallization isotherm of the samples, after the levels of trisaturated triacylglycerols decreased and disaturated–monounsaturated and monosaturated–diunsaturated triacylglycerol contents increased, due to the randomization of fatty acids. The modification in the triacylglycerol composition promoted greater miscibility between the HOSO and FHPO fractions, creating new application possibilities for the food industry.     

Development of a rheological method to characterize palm oil crystallizing under shear

To follow palm oil crystallization under shear, a new rheological method was developed. This method can be split up into two parts: In the first part, continuous shear is applied for a pre‐defined period and crystallization is monitored by measuring the apparent viscosity as a function of isothermal time under shear. In the second part, shear is halted and oscillation is applied during 30 s, thus recording moduli and phase angle. These moduli and phase angle are then characteristic of a sample crystallized under shear during this pre‐defined period. After repeating this procedure for increasing shearing periods in the first part, complex modulus and phase angle were plotted as a function of isothermal time under shear. The thus obtained results were compared with crystallization data obtained via time‐resolved X‐ray diffraction and polarized light microscopy.     

Enzymatic Glycerolysis of Palm and Palm Kernel Oils

Glycerolysis of palm and palm kernel oils were carried out using commercial lipases from Candida antarctica (Novozym 435) and Mucor miehei (Novozym 388) as catalyst (500 units lipase/g oil) at 40°C and with an oil:glycerol molar ratio of 1:2 in a solvent-free system. Novozym 435 catalyzed the glycerolysis of palm and palm kernel oils giving reaction products in similar compositions. Partial acylglycerols contents of the glycerolysis products obtained from palm and palm kernel oils were 64% (wt) and 66% (wt), respectively. However, partial acylglycerols contents of the glycerolysis products obtained from palm and palm kernel oils conducted with Novozym 388 as catalyst at the same conditions were 44% (wt) and 56% (wt), respectively. On the other hand, free fatty acid contents of the glycerolysis products of palm and palm kernel oils obtained using Novozym 388 were higher, 25-30% (wt), than those obtained by Novozym 435, 4-5% (wt). The monoacylglycerols fraction with the highest content of oleic acid, 62.7% (wt), was obtained from the palm kernel oil glycerolysis reaction catalyzed by Novozym 435.     

Enzymatic Glycerolysis of Palm and Palm Kernel Oils

Glycerolysis of palm and palm kernel oils were carried out using commercial lipases from Candida antarctica (Novozym 435) and Mucor miehei (Novozym 388) as catalyst (500 units lipase/g oil) at 40°C and with an oil:glycerol molar ratio of 1:2 in a solvent-free system. Novozym 435 catalyzed the glycerolysis of palm and palm kernel oils giving reaction products in similar compositions. Partial acylglycerols contents of the glycerolysis products obtained from palm and palm kernel oils were 64% (wt) and 66% (wt), respectively. However, partial acylglycerols contents of the glycerolysis products obtained from palm and palm kernel oils conducted with Novozym 388 as catalyst at the same conditions were 44% (wt) and 56% (wt), respectively. On the other hand, free fatty acid contents of the glycerolysis products of palm and palm kernel oils obtained using Novozym 388 were higher, 25–30% (wt), than those obtained by Novozym 435, 4–5% (wt). The monoacylglycerols fraction with the highest content of oleic acid, 62.7% (wt), was obtained from the palm kernel oil glycerolysis reaction catalyzed by Novozym 435.     

Consumption of High-Oleic Soybean Oil Improves Lipid and Lipoprotein Profile in Humans Compared to a Palm Oil Blend: A Randomized Controlled Trial

Partially hydrogenated oils (PHO) have been removed from the food supply due to adverse effects on risk for coronary heart disease (CHD). High-oleic soybean oils (HOSBO) are alternatives that provide functionality for different food applications. The objective of this study was to determine how consumption of diets containing HOSBO compared to other alternative oils, with similar functional properties, modifies LDL cholesterol (LDLc) and other risk factors and biomarkers of CHD. A triple-blind, crossover, randomized controlled trial was conducted in humans (n = 60) with four highly-controlled diets containing (1) HOSBO, (2) 80:20 blend of HOSBO and fully hydrogenated soybean oil (HOSBO+FHSBO), (3) soybean oil (SBO), and (4) 50:50 blend of palm oil and palm kernel oil (PO + PKO). Before and after 29 days of feeding, lipids/lipoproteins, blood pressure, body composition, and markers of inflammation, oxidation, and hemostasis were measured. LDLc, apolipoprotein B (apoB), NonHDL-cholesterol (HDLc), ratios of total cholesterol (TC)-to-HDLc and LDLc-to-HDL cholesterol, and LDL particle number and small LDL particles concentration were lower after HOSBO and HOSBO+FHSBO compared to PO (specific comparisons p < 0.05). Other than TC:HDL, there were no differences in lipid/lipoprotein markers when comparing HOSBO+FHSBO with HOSBO. LDLc and apoB were higher after HOSBO compared to SBO (p < 0.05). PO + PKO increased HDLc (p < 0.001) and apolipoprotein AI (p < 0.03) compared to HOSBO and HOSBO+FHSBO. With the exception of lipid hydroperoxides, dietary treatments did not affect other CHD markers. HOSBO, and blends thereof, is a PHO replacement that results in more favorable lipid/lipoprotein profiles compared to PO + PKO (an alternative fat with similar functional properties).     

Thermal Degradation Kinetics of Carotenoids in Palm Oil

In the present work, a detailed study is performed for carotene thermal degradation in palm oil at four temperatures ranging from 170 to 230 °C. The heating process was carried out with injection of nitrogen, and the samples were collected every 20 min during a total heating period of 140 min. HPLC analysis was conducted to monitor the carotenoids and tocols variations over the heating time at each temperature. The experimental data were then compared to literature data concerning carotenoids thermal degradation. The thermal degradation kinetics of carotenoids in palm oil followed an order superior to 1. The dependence of constant rates with temperature obeyed the Arrhenius relationship. The activation energy for the carotenoids thermal degradation in palm oil was found to be 109.4 kJ/mol.     

Synthesis and Thermal Characterization of Polyurethane/Clay Nanocomposites Based on Palm Oil Polyol

Polyurethanes (PUs) are very versatile polymeric materials with a wide range of physical and chemical properties. PUs also have desirable properties, such as high abrasion resistance, tear strength, shock absorption, flexibility, and elasticity. Although they have poor thermal stability, it can be improved by using treated clay.

The objective of the present work is to study the thermal stability of polyurethane, polyurethane/montmorillonite (PU CTAB-mont 3% wt), and polyurethane/montmorillonite containing moca (PU Moca CTAB-mont 3% wt) nanocomposites based on palm oil polyol.

The interest of investigating the synthesis of polyurethane/clay nanocomposites based on palm oil polyol is to explore the use of palm oil polyol to partially replace petrochemical-based polyol.

Polyurethane/clay nanocomposites were prepared by a pre-polymer method and evaluated by Fourier Transform Infrared Spectra (FTIR) to determine micro-domain structures of segmented PU, PU CTAB-mont 3% wt, and PU Moca CTAB-mont 3% wt. The morphology of the nanocomposites was characterized by X-ray diffraction (X-RD), and flame retardant was investigated with thermogravimetric analysis (TGA). The result showed that in comparison with the virgin polyurethane, adding clay and moca demonstrated better thermal stability.     

Effects of Pilot Plant-Scale Ultrasound on Palm Oil Separation and Oil Quality

The effects of ultrasonic standing waves on palm oil separation of ex-screw press feed from the mesocarp of the palm oil fruit, oil recovery and oil quality were determined. The ex-screw press feed at 85 °C was pumped simultaneously into two identical vessels. One vessel was the control (non-ultrasound) and the other vessel (ultrasound) was fitted with two 400 kHz transducer plates operating at 13.4 kJ/kg, which were placed in direct contact with the feed. Oiling-off by gravity settling occurred at faster rates after sonication. The total recoverable oil after 30 min gravity settling and upon centrifuging the underflow sludge (remaining colloidal fraction) at 1000×g was higher after sonication. Total recoverable oil was 30.7 ± 2.9 % and 43.5 ± 8.6 % (w/w original feed basis) for the non-sonicated and sonicated samples respectively. Sonication reduced the oil content of the sludge ex-centrifuge, demonstrating that higher recovery of palm oil was obtained with ultrasound application. Sonication did not affect the DOBI (deterioration of bleachability index) value, and vitamin E and free fatty acid contents of the separated oil. High-frequency ultrasound enhances the separation rate of palm oil and increases oil recovery without compromising oil quality.     

Isothermal Crystallization of Palm Oil-Based Fats with and without the Addition of Essential Oils

The objective of study was to evaluate the crystallization behavior of palm oil-based fats processed with and without the addition of essential oils (5% w/w) obtained from the flowers (EsOF) and stems (EsOS) of Pituranthos scoparius. Palm oil (PO) and a mixture of PO, soybean oil, and sunflower oil (Mix) were tested. The addition of the essential oils did not change the melting points of the fats but affected their crystallization behavior. A delay in crystallization was observed, evidenced by lower crystallization rates, and lower solid fat contents. This delay was comparable in the samples crystallized with EsOF and EsOS for the PO samples but EsOF was more efficient at delaying crystallization in the Mix sample. EsOF generated a less organized crystalline network in both samples (lower enthalpy values) while EsOS generated a more organized crystalline network (high enthalpy values) when used in the Mix sample. The addition of EsO also affected the crystal microstructure in some cases. While a slight increase in crystal size was observed for some PO samples crystallized with EsOF, no change or a decrease in crystal size was observed for the samples crystallized with EsOS. A slight decrease in crystal size was observed for Mix samples crystallized with EsOF while no effect was observed for these samples crystallized with EsOS. Results from this study show that these essential oils can be used as natural additives to modify the crystallization of fats for food applications and therefore widen their functional properties.     

Continuous Methanolysis of Palm Oil Using a Liquid–Liquid Film Reactor

A system for the continuous methanolysis of palm oil using a liquid–liquid film reactor (LLFR) was developed and characterized. This reactor is a co-current, constant diameter (0.01 m), custom-made packed column where the mass transfer area between the partially miscible methanol-rich and vegetable oil-rich phases is created in a non-dispersive way, without the intervention of mechanical stirrers or ultrasound devices. An increase in contact area between phases enhances reaction rate while the absence of small, dispersed droplets of one phase into the other diminishes the settling time at the end of the reaction. In this study variations on the concentration of catalyst (sodium hydroxide), flow rate of palm oil and normalized length of the reactor (L/L _max) were explored, keeping constant both the methanol to oil molar ratio and the temperature of the reaction (6:1 and 60 °C). The best experimental results with a reactor of 1.26 m (L/L _max = 1.0) showed a conversion of palm oil of 97.5% and a yield of methyl esters of 92.2% of the theoretical yield, when the mass flow rate and the residence time of the palm oil were 9.0 g min⁻¹ and 5.0 min, respectively. To determine the mean residence time and the degree of axial mixing in the reactor, a residence time distribution (RTD) study was performed using a step-function input. The dispersion model appears to fit well the RTD experimental data.     

棕榈酸化油制备生物柴油的工艺优化研究

试验研究了以棕榈酸化油与甲醇为原料,在催化剂(浓硫酸)的作用下,通过酯化反应制备生物柴油。采用单因素试验和正交优化试验,考察反应温度、搅拌速率、醇油摩尔比和催化剂用量(与原料油质量比)对酯化反应收率的影响。确定最佳反应条件为反应温度为55℃,搅拌速率为200 r/min,醇油摩尔比为7:1,催化剂用量为2.0%,且在该条件下酯化效率为93.9%。