Palm Mid Fraction Research Articles

Hydrogenation of Malaysian Palm Mid Fraction on Pricat Nickel Catalyst Using Pilot and Industrial Units

Palm mid fraction produced from Malaysian palm olein was hydrogenated using industrial catalyst (PRICAT 9910) on both pilot and industrial units. Effects of hydrogenation parameters, including temperature, catalyst concentration, reaction time, and circulation rate on final fatty acid composition and trans-fatty acid content were investigated. Mass transfer limitations were indicated particularly in the industrial plant runs. Mass transfer coefficient in the gas–liquid transfer was identified for various circulation rates. The combined mass transfer resistance at the liquid–solid interface and within the catalyst pellet was calculated as a function of different temperatures and circulation rates.

Studies of isothermal crystallisation kinetics of sunflower hard stearin-based confectionery fats

The crystallisation and polymorphic properties of three sunflower hard stearins (SHSs) and cocoa butter equivalents (CBEs) formulated by blending SHSs and palm mid fraction (PMF) were studied and compared with those from cocoa butter (CB), to explore their possibilities as confectionery fats. The isothermal crystallisation kinetics of these fats were examined by pNMR and DSC at three different temperatures. All samples studied displayed a two-step crystallisation profile that could be fitted to an exponential-Gompertz equation. Stop-and-return DSC studies showed that SHSs and CBEs exhibited different crystallisation mechanisms according to their triacylglycerol composition, with a quick formation of metastable crystals, followed by a polymorphic transition to the more stable β or β′ forms. X-ray diffraction (XRD) was used to investigate the polymorphic forms of tempered SHSs and CBEs in the long term. In all cases the resulting fats displayed short spacing patterns associated with β polymorphism. These formulations based on SHSs and PMF met all the requirements to be considered as CBEs; therefore they could be used as an alternative to traditional confectionery fats.

Development of a Coconut‐ and Palm‐Based Fat Blend for a Cookie Filler

AbstractThirteen fat blends intended for cookie filler (CF) production that consist of 20–70 % palm mid‐fraction (PMF), 20–70 % virgin coconut oil (VCO), and 0–10 % palm stearin (POs) were developed based on the solid fat contents (SFC) of the fat portions extracted from five commercial CF samples: A, B, C, D, and E. A mixture design was applied for fat blend optimization, and the combination that best approached the target SFC values was composed of 70 % PMF, 20 % VCO, and 10 % POs. The optimized coconut‐ and palm‐based fat blend (O‐CP) exhibited a steeper SFC profile, with 8.2 % (±0.2) SFC at 25 °C (room temperature) and 0.2 % (±0.2) SFC at 37 °C (body temperature); lower slip melting point of 34.0 °C (±0.0); and a lower iodine value (IV) of 40.25 g/100 g (±1.04). In addition, O‐CP contained higher proportions of medium‐chain fatty acids (MCFA) and lauric acid (C12:0) of 3.2 % (±0.18) and 9.7 % (±0.43), respectively. In terms of its thermal profile, O‐CP showed no significant difference in terms of its crystallization range, 49.7 °C (±2.66) with the exception of sample C, but it exhibited a smaller melting range, 65.8 °C (±1.47), compared to the fat portions of the commercial samples. The ranges represented the span between the onset and offset temperatures of both crystallization and melting profiles as determined by differential scanning calorimetry.

Effect of fat types on the structural and textural properties of dough and semi-sweet biscuit.

Fat is an important ingredient in baking products and it plays many roles in providing desirable textural properties of baking products, particularly biscuit. In this study, the effect of fat types on dough rheological properties and quality of semi-sweet biscuit (rich tea type) were investigated using various techniques. Texture profile and extensibility analysis were used to study the dough rheology, while three-point bend test and scanning electron microscopy were used to analyse the textural characteristics of final product. TPA results showed that the type of fat significantly influenced dough textural properties. Biscuit produced with higher solid fat oil showed higher breaking force but this was not significantly different when evaluated by sensory panel. Scanning electron microscopy showed that biscuit produced with palm mid-fraction had an open internal microstructure and heterogeneous air cells as compared to other samples.

Evaluation of high oleic-high stearic sunflower hard stearins for cocoa butter equivalent formulation.

Cocoa butter equivalents (CBEs) are produced from vegetable fats by blending palm mid fraction (PMF) and tropical butters coming from shea, mango kernel or kokum fat. In this regard, high oleic-high stearic (HOHS) sunflower hard stearins from solvent fractionation can be used in CBE production since their compositions and physical properties are similar to those found in the above-mentioned tropical butters. In this work, three sunflower hard stearins (SHS) ranging from 65% to 95% of disaturated triacylglycerols and a shea stearin (used as reference) were blended with PMF to evaluate their potential use in CBEs formulation. Isosolid phase diagrams of mixtures of PMF/SHS showed eutectic formation for SHS 65 and SHS 80, but monotectic behaviour with softening effect for SHS 95. Three CBEs from SHS and shea stearin were formulated according to phase behaviour diagrams and solid fat content data at 25 °C. Isosolid phase diagrams of mixtures of these CBEs with cocoa butter showed no eutectic behaviour. Therefore, CBEs elaborated from SHS exhibited full compatibility with cocoa butter.

팜중부유를 이용한 대칭형 Palmitoyl-Oleoyl-Stearoyl Triacylglycerol의 효소적 합성 반응 연구

본 연구에서는 palm mid fraction(PMF)와 stearic ethyl ester를 기질로 Lipozyme TLIM을 이용한 에스테르 교환반응을 실시하였으며 기질의 몰 비율과 효소양 및 시간에 따른 TAG 조성 변화와 함께 POS 구성율 및 acyl migration 정도를 알아보았다. sn-2 위치에서의 주요 지방산 조성 변화는 몰 비율과 효소양, 반응시간이 증가할수록 C18:1은 점차 감소하였고, C16:0과 C18:0은 증가함을 알 수 있었다. 이와 같은 변화는 특히 반응시간이 증가함에 따라 두드러지게 나타났으며 acyl migration 생성과 관계가 깊은 것으로 예측되었다. 그 결과 총 포화지방산의 함량은 최고 37.4 area%까지 증가한 수치를 보였다. 반응 합성물의 주요 TAG 조성으로는 POP, POS, SOS와 같은 대칭형 구조의 TAG가 확인되었으며 반응이 진행됨에 따라 POP는 감소하고 POS가 증가하는 경향을 보였다. Acyl migration과 POS 함량을 고려하였을 때 몰 비율 1:2, 효소양 3 wt%, 5시간 반응 조건에서 POS는 53.5 area%의 높은 함량을 보였으며 이때 총 포화지방산 함량은 반응 전 11.9 area%와 비교하여 약 2배 증가한 23.1 area%를 나타내었다. 한편, 전체 반응 조건 중 가장 높은 POS 함량은 55.4 area%의 수치를 보였는데, 이후 몰 비율과 효소양의 증가와 더불어 반응시간이 지속되었음에도 불구하고 POS는 오히려 감소하는 것을 확인할 수 있었다. 또한 반응이 진행되면서 acyl migration에 의해 sn-2 위치에 palmitic acid와 stearic acid가 전이된 PPS, PSS, SSS와 같은 TAG의 생성도 증가함을 알 수 있었다.

Enzymatic Interesterification of Palm Oil and Fractions: Monitoring the Degree of Interesterification using Different Methods

AbstractInteresterification is an important modification technique for fats and oils resulting in the redistribution of the fatty acids among the glycerol backbone and thus changing the physico‐chemical properties of the modified fat. In this study palm oil, palm olein and soft palm mid fraction (PMF) were subjected to both enzymatic (batchwise) and chemical interesterification. The reaction products were characterized before, during and after interesterification by HPLC, pulsed NMR (p‐NMR) and differential scanning calorimetry (DSC). Interesterification led to more uniform triacylglycerol (TAG) compositions with smaller differences in final physico‐chemical properties between the studied substrates. The degree of interesterification was evaluated on the basis of TAG composition and solid fat content (SFC). Significant differences between both methods were observed. The degree of interesterification based on SFC is therefore a better tool to evaluate the rate constant of the reaction as the TAG composition method does not take into consideration the formation of positional isomers at the end of the enzymatic process.

Effect of hydrogenation temperature on the palm mid-fraction fatty acids composition and conversion

Palm mid fraction (PMF) was hydrogenated using Armfield hydrogenation pilot plant unit. Effects of hydrogenation temperature on the total conversion and selectivity were investigated. Noticeable effect of hydrogenation temperature on the reaction conversion was found. The values of reaction conversion at temperatures 99 and 130 °C were found to be considerably lower, when compared to those at temperatures 137 and 149 °C. The alteration on fatty acid composition had been studied at varying temperature and other parameters were kept constant. It can also be observed that the trans-fatty acids (TFA) content in the PMF samples hydrogenated at temperature ranges 130–137 °C, and 137–149 °C were found to be 0.197 and 0.186, respectively. Effect of reaction temperature on mass transfer resistance from the hydrogen bubble to the catalyst surface was estimated. The obtained results clarify that the volumetric mass transfer coefficient was increased around 140% by increasing the reaction temperature from 99 to 130 °C.

Physico-chemical properties of various palm-based diacylglycerol oils in comparison with their corresponding palm-based oils

Palm-based diacylglycerol (P-DAG) oils were produced through enzymatic glycerolysis of palm kernel oil (PKO), palm oil (PO), palm olein (POL), palm mid fraction (PMF) and palm stearin (PS). High purity DAG (83–90%, w/w) was obtained and compared to palm-based oils (P-oil) had significantly (P<0.05) different fatty acid composition (FAC), iodine value (IV) and slip melting point (SMP). Solid fat content (SFC) profiles of P-DAG oils as compared to P-oils had less steep curves with lower SFC at low temperature range (5–10°C) and the higher complete melting temperatures. Also, P-DAG oils in contrast with P-oils showed endothermic as well as exothermic peaks with higher transition temperatures and significantly (P<0.05) higher crystallisation onsets, heats of fusion, and heats of crystallisation. Crystal forms for P-DAG oils were mostly in the β form.

Physical and Sensory Attributes of a trans‐Free Spread Formulated with a Blend Containing a Structured Lipid, Palm Mid‐Fraction, and Cottonseed Oil

AbstractPhysical and sensory attributes of an experimental trans‐free margarine spread (MG‐X) and two commercial margarine spreads (MG‐A and MG‐B) were studied. The trans‐free margarine spread was formulated with a blend containing a structured lipid (SL) synthesized by reacting canola oil with 40% stearic acid (w/w), palm mid‐fraction (PMF), and cottonseed oil (CTO). No trans fatty acids were detected in MG‐X, whereas the trans fatty acid contents of MG‐A and MG‐B were 0.3 and 3.7% (w/w), respectively. MG‐X was considerably firmer than MG‐A and MG‐B, less cohesive, and its adhesiveness was intermediate between those of MG‐A and MG‐B. MG‐X’s stability to syneresis was also intermediate between those of MG‐A and MG‐B. Sensory evaluation showed that MG‐X was comparable to MG‐A in terms of spreadability and texture only, but was significantly different from MG‐B in all attributes.

Scanning Microbeam Small-Angle X-ray Diffraction Study of Interfacial Heterogeneous Crystallization of Fat Crystals in Oil-in-Water Emulsion Droplets

We performed scanning microbeam small-angle X-ray diffraction (micro-SAXD) experiments, differential scanning calorimetry (DSC) analysis, and optical microscopic observation of palm mid fraction (PMF) crystals in oil-in-water emulsion droplets. The scanning micro-SAXD experiment was performed by irradiating a synchrotron radiation X-ray microbeam having an area of 5 x 5 microm(2) onto different positions on a 50 microm diameter emulsion droplet after the crystallization of PMF by chilling the emulsion at 5 degrees C. The micro-SAXD patterns were recorded with a two-dimensional (2D) detector, which enabled spatial analysis of polymorphic structures and the orientation of lamella planes of PMF crystals at different positions inside the emulsion droplet. Particular attention was paid to compare the crystallization of PMF in two types of emulsion droplets, hydrophilic polyoxyethylene sorbitan mono-oleate (Tween 80) alone (Tween 80 emulsion) and Tween 80 and hydrophobic sucrose palmitic acid oligoester (P-170) (Tween 80+P-170 emulsion). The DSC study revealed that the PMF crystallization temperature in the Tween 80+P-170 emulsion droplets increased by 3 degrees C compared to that of the Tween 80 emulsion because of the effects of the P-170 additive in promoting PMF crystallization. The micro-SAXD studies revealed the following results. (1) The lamella planes of PMF crystals near the outer edges of the droplet in the Tween 80+P-170 emulsion were mostly parallel to an oil-water interface, whereas the lamella planes of PMF crystals were not always aligned with the oil-water interface in the Tween 80 emulsion droplet. (2) The degree of orientation of the lamellar planes of PMF crystals, which was evaluated from the values of full width at half-maximum of 2D micro-SAXD patterns with respect to azimuthal angle extension, was remarkably higher in the Tween 80+P-170 emulsion than in the Tween 80 emulsion. (3) Polymorphic transformation of PMF from alpha to beta' in the Tween 80+P-170 emulsion was retarded compared to that in the Tween 80 emulsion. These results confirmed that the P-170 additive caused interfacial heterogeneous nucleation through hydrophobic interactions at the oil-water interfaces in the emulsion, which subsequently influenced the arrangements of fat crystals so that the lamellar planes of fat crystals were parallel to the oil-water interface.

효소적 Acidolysis를 이용한 Stearic Acid 함유 팜중부유의 개질

The acidolysis was performed to produce structured lipid with palm mid fraction (PMF) and stearic acid for 7, 24, and 36 hr at 70 o C. The reaction was catalyzed by lipozyme TLIM (immobilized lipase from Thermonyces lanuginosa, amount of 10% and 20% by weight of total substrates) in the shaking water bath. The reaction conditions for maximum incorporation of stearic acid on the structured lipid were obtained when molar ratio of PMF and stearic acid was 1:2; concentration of lipozyme TLIM was 20wt%; reaction temperature was 70 o C; and reaction time was 36 hr. After reaction under this condition, incorporation of stearic acid in the structured lipid was obtained up to 36.3% while the major components of triacylglycerol were 1,2-dipalmitoyl-3-stearoylglycerol (PPS, 28.19 area%), 1-palmitoyl-2-oleoyl-3-stearoylglycerol (POS/PSO, 20.70 area%) and 1-palmitoyl-2,3-distearoylglycerol (PSS, 18.13 area%). However, the fatty acid composition at the sn-2 position suggested that the positional specificity of lipozyme TLIM was not observed due to the acyl migration.

Optimization of Solid Fat Content and Crystal Properties of a trans-Free Structured Lipid by Blending with Palm Midfraction

The optimization of solid fat content (SFC) and crystal properties of trans-free structured lipids (SL) synthesized by incorporating stearic acid into canola oil was investigated. The SLs were blended with varying amounts of palm midfraction (PMF). The SFC and crystal polymorphism were improved. The addition of sucrose stearate (S-170), sorbitan tristearate (STS), and distilled monoglycerides (DMG) to one of the blends, SL40:PMF (70:30, w/w), did not improve crystal polymorphism but had significant effects on crystal morphology. The emulsifiers significantly delayed crystal growth, resulting in smaller crystal sizes as compared to the control. They were unable to inhibit the formation of granular crystals (30-140 microm), which are undesirable in margarine, after 4 weeks of storage at 0 degrees C. Blends treated with S-170 and STS showed many small evenly distributed crystals interspersed with large crystal aggregates (after 4 weeks of storage), whereas the blend treated with DMG and the control showed irregularly shaped globular crystals, also interspersed with large crystal aggregates. However, these crystal aggregates were not observed upon visual and physical examination and may therefore not impart the sensory properties of the finished products negatively.

Application of alpha-tocotrienol for detection of palm mid-fraction in dark chocolate formulation

Following model studies, the detection of palm mid-fraction (PMF) added to cocoa butter (CB) in chocolate formulations was investigated. Different levels of PMF (0–25%, CB basis) were added to CB in chocolate. High performance liquid chromatography was then used to detect the presence of PMF in chocolate using α-tocotrienol as an indicator. The results, in line with the model studying indicated that increasing the amount of PMF added to CB resulted in a significant (P < 0.05) increase in the concentration of α-tocotrienol in chocolate; a linear plot (R 2 = 0.9837) was obtained with standard error of 1.986. A validation test was conducted to verify the equation obtained from the regression analysis. The high R 2-value obtained indicated a good accuracy, reflecting a close relationship between experimental and theoretically predicted values. The applied indicator performed well beyond the level of the statutory limit of 5% PMF addition on a chocolate basis that verified the previously studied model.

Detection and quantification of palm mid‐fraction in a chocolate model system

SummaryThe tocopherol and tocotrienol compositions of the genuine cocoa butter (CB) and palm mid‐fraction (PMF) were investigated to introduce a more reliable indicator in detecting PMF in CB. The results suggested that the α‐tocotrienol data presented could be utilised for the detection of the PMF admixture to CB. The PMF was added to CB at different levels. HPLC was used to detect the presence of PMF admixture to CB using α‐tocotrienol as an indicator. The results derived from the model system indicated that increasing the PMF amount at 0–15% to CB resulted in an increase in the concentration of the α‐tocotrienol significantly (P &lt; 0.05). The addition of PMF amount more than 15% did not have any effect on the α‐tocotrienol concentration. A linear plot with a high correlation of 0.9967 was obtained with SE of 1.527. The high correlation obtained indicated good accuracy, reflecting a close relationship between experimental and theoretical predicted value.

Phase Composition During Palm Olein Fractionation and its Effect on Soft PMF and Superolein Quality

AbstractRefined palm olein was dry fractionated via three different cooling programs on laboratory‐scale fractionation equipment. The enrichment and depletion of the main triacylglycerols in the liquid and solid phase was plotted as a function of the crystallization degree of the oil. It was shown that for the given conditions and palm olein composition, the initial crystals mainly consisted of PPP, diacylglycerols, POP and PLP. At higher crystallization degrees, a sharp viscosity increase in the crystal suspension was primarily related to an obvious decrease of POP but also of POS in the recovered superolein, while the general crystallization rate of the system remained unchanged. Rather than a change in crystallization rate of POP, a change in the ratio between the crystallizing monounsaturated triacylglycerols is linked with the high viscosity of the crystal slurry. For a comparable degree of crystallization, the superolein of the more viscous crystal slurry, obtained through a membrane press filtration up to 15 bar, was more unsaturated than the superolein filtered from the less viscous slurry. Consequently, the high unsaturation in the corresponding soft palm mid fraction is only the result of an incomplete phase separation, and not due to an increased intersolubility of unsaturated triacylglycerols in the crystals.

Retardation of crystallization-induced destabilization of PMF-in-water emulsion with emulsifier additives

An oil-in-water (O/W) emulsion, in which the oil phase is semi-solid fat, is easily destabilized when stored below the crystallization temperature of the oil phase. Such destabilization, characterized by loss of fluidity at chilled temperature and oil–water separation after re-heating, is caused by inter-droplet bridging of fat crystals protruding out of the emulsion droplets. In the present study, we found that the simultaneous use of additives of highly hydrophobic sucrose oligoester (SOE; P-170) and highly hydrophilic SOE (P-1670) containing palmitic acid moiety remarkably retarded the crystallization-induced destabilization of the O/W emulsion that contains palm-mid-fraction (PMF) as the oil phase. Without the additives, destabilization occurred when the emulsion was cooled from 60 to 0 °C and kept at 0 °C for 1 day. Microscopic observation revealed that destabilization was caused by coalescence of the oil droplets, which was triggered by the growth of needle-shaped PMF crystals protruding out of the emulsion membranes. However, the addition of P-170 to PMF increased the crystallization temperature of PMF and at the same time retarded the destabilization. Furthermore, the simultaneous addition of P-170 and P-1670 retarded the crystallization-induced destabilization even more. Optical observation, DSC, and synchrotron radiation X-ray diffraction measurements indicated that the P-170 additive enhanced interfacial heterogeneous crystallization to form tiny PMF crystals in the droplets, and that the P-1670 additive retarded morphological change of the PMF crystals into long needle shapes in association with polymorphic transformation from α to β′.

Influences of fatty acid moiety and esterification of polyglycerol fatty acid esters on the crystallization of palm mid fraction in oil-in-water emulsion

We examined the crystallization of palm mid fraction (PMF) in oil-in-water (O/W) emulsion, after adding polyglycerol fatty acid esters (PGFEs). We employed ultrasonic velocity measurements and DSC techniques, with special emphases on the influences of fatty acid moiety and esterification of PGFE. Twelve types of PGFEs were examined as additives. PGFEs have a large hydrophilic moiety composed of 10 glycerol molecules to which palmitic, stearic and behenic acids were esterified as the fatty acid moiety with different degrees of esterification. Crystallization temperature ( T c) of PMF remarkably increased with increasing concentrations of the PGFEs as the chain length of the fatty acid moiety increased, and the PGFE became more hydrophobic in accordance with increasing degree of esterification. We observed that the heterogeneous nucleation of PMF in the O/W emulsion was activated at the oil–water interface, where the template effect of very hydrophobic long saturated fatty acid chains of the PGFE might play the main role of heterogeneous nucleation.

Ultrasonic studies of the crystallization behavior of two palm fats O/W emulsions and its modification

Based on the difference between the speed of sound in solids and liquids, an ultrasonic velocity technique was employed to monitor the phase transition, nucleation and crystal growth of two palm oils dispersed as oil-in-water (O/W) emulsions. The O/W emulsions of palm mid-fraction (PMF) and palm kernel oil (PKO) crystallized at 12 and 0 °C, respectively. The degree of supercooling of PMF emulsion was 18 °C, while that of PKO emulsion was 28 °C. The effects of different hydrophobic emulsifier additives on the interfacial heterogeneous nucleation, induced at the oil/water interface of emulsion droplets, and crystal growth were studied by monitoring the sound velocity ( V) during isothermal crystallization. Sucrose oligoesters (SOEs) having stearic (S-170) and palmitic (P-170) fatty acid chains accelerated nucleation, yet SOEs having short chains such as lauric (L-170) showed no effect in the two fats. A polyglycerine ester (DAS-750) had a lesser and different effect on the nucleation of PKO compared to PMF. Moreover, the crystal growth was retarded in the two oils at different degrees by the addition of S-170. Solubility measurements indicated that the solubility degree of DAS-750 was more than that of S-170. In addition, the solubility of DAS-750 was higher in PKO than in PMF. The effects of the additives were thus discussed in terms of their molecular structure in relation to the oil phase composition.

Fourier transform infrared spectroscopy and chemometrics as a tool for the rapid detection of other vegetable fats mixed in cocoa butter

AbstractThe Fourier transform infrared (FTIR) technique in combination with multivariate data evaluation was used to analyze a wide variety of cocoa butters (CB), cocoa butter equivalents (CBE), and mixtures thereof. The sample set consisted of 14 CB (10 pure from various geographical origins and 4 commercial mixtures), 18 CBE (12 mixtures and 6 pure CBE from kokum, illipé, and palm midfraction), and 154 mixtures of CB with CBE at various concentrations (ranging from 5 to 20%). A total of 192 samples were analyzed in triplicate. All CB and CBE were shown to have very characteristic FTIR spectra that gave highly reproducible fingerprints. The main vibrational modes were also elucidated. FTIR can easily be employed to distinguish between pure CB and pure CBE. With prior knowledge of which cocoa butter is present in mixtures, FTIR can be applied to distinguish between CB mixed with CBE at the 10 and 20% levels (corresponding to about 2 and 5% of CBE in chocolate). However, the study revealed that a single “global” statistical model (multilayer perceptron, radial basis functions, or partial least square regression) was not able to predict the precise level of addition. The FTIR approach detailed here shows great potential as a rapid screening method for distinguishing between pure vegetable fats and, we believe, could be extended to investigate mixtures of CB and CBE by the establishment of a database.