Composition and thermal profile of crude palm oil and its products

Gas-liquid chromatography and high-performance liquid chromatography (HPLC) were used to determine fatty acids and triglyceride (TG) compositions of crude palm oil (CPO), refined, bleached, and deodorized (RBD) palm oil, RBD palm olein, and RBD palm stearin, while their thermal profiles were analyzed by differential scanning calorimeter (DSC). The HPLC chromatograms showed that the TG composition of CPO and RBD palm oil were quite similar. The results showed that CPO, RBD palm oil, RBD olein, and superolein consist mainly of monosaturated and disaturated TG while RBD palm stearin consists mainly of disaturated and trisaturated TG. In DSC cooling thermograms the peaks of triunsaturated, monosaturated and disaturated TG were found at the range of −48.62 to −60.36, −25.89 to −29.19, and −11.22 to −1.69°C, respectively, while trisaturated TG were found between 13.72 and 27.64°C. The heating thermograms of CPO indicated the presence of polymorphs β₂′, α, β₂′, and β₁. The peak of CPO was found at 4.78°C. However, after refining, the peak shifted to 6.25°C and became smaller but more apparent as indicated by RBD palm oil thermograms. The heating and cooling thermograms of the RBD palm stearin were characterized by a sharp, high-melting point (high-T) peak temperature and a short and wide low-melting point (low-T) peak temperature, indicating the presence of occluded olein. However, for RBD palm olein, there was only an exothermic low-T peak temperature. The DSC thermograms expressed the thermal behavior of various palm oil and its products quite well, and the profiles can be used as guidelines for fractionation of CPO or RBD palm oil.     

Fractionation of menhaden oil and partially hydrogenated menhaden oil: Characterization of triacylglycerol fractions

Menhaden oil (MO) and partially hydrogenated menhaden oil (PHMO) were dry-fractionated and solvent-fractionated from acetone. After conversion to fatty acid methyl esters, the compositional distribution of saturated, monounsaturated, trans, and n−3 polyunsaturated fatty acids (PUFA) in the isolated fractions was determined by gas chromatography. Acetone fractionation of MO at −38°C significantly increased the n−3 PUFA content in the liquid fractions over that of starting MO (P<0.05). For PHMO, liquid fractions obtained by low-temperature crystallization (−38, −18, and 0°C) from acetone showed significant increases (P<0.05) in monounsaturated fatty acid (MUFA) content over that of the starting PHMO. For selected MUFA-enriched fractions, reversed-phase high-performance liquid chromatography (HPLC) was used to separate, isolate, and characterize the major triacylglycerol (TAG) molecular species present. Thermal crystallization patterns for these fractions also were determined by differential scanning calorimetry (DSC). The results demonstrated that under the appropriate conditions it is possible to dry-fractionate or solvent-fractionate MO and PHMO into various solid and liquid fractions that are enriched in either saturated, monounsaturated, polyunsaturated, or the n−3 classes of fatty acids. Moreover, characterization of these TAG fractions by reversed-phase HPLC gives insight into the compositional nature of the TAG that are concentrated into the various fractions produced by these fractionation processes. Finally, the DSC crystallization patterns for the fractions in conjunction with their fatty acid compositional data allow for the optimization of the fractionation schemes developed in this study. This information allows for the production of specific TAG fractions from MO and PHMO that are potentially useful as functional lipid products.     

Isopropanol fractionation of butter oil and characteristics of fractions

Fractionation of butter oil from isopropanol and characterization of the chemical composition and the melting properties of the fractions obtained have been investigated. Butter oil was fractionated from isopropanol (1∶4 wt/vol) at 15 to 30°C. The yields of stearins and oleins were dependent on the temperature employed during fractionation. Thus, 24.8 to 48.9% of stearins and 51.5 to 75.2% of oleins could be obtained as the crystallization temperature varied from 15 to 30°C. The stearin fractions displayed a distinct variation in the fatty acid compositions. The palmitic acid content of the stearin fractions varied from 39.1 to 44.0%, and that of stearic from 15.1 to 16.8%, respectively. The olein fractions contained 43.2% stearic acid, and 2.4 to 2.8% palmitoleic acid (C16∶1). The solid fat content values of the stearin fractions obtained were 62–67, 39–50, and 21–25 at 10, 20, and 30°C, respectively. From the results, it is evident that anhydrous milk fat can be fractionated at relatively high temperatures from isopropanol to produce stearin and olein fractions of specific composition and properties.     

Composition and thermal properties of cattle fats

The physical‐chemical properties, fatty acid composition and thermal properties of cattle subcutaneous, tallow and intestinal fats were determined. Subcutaneous fat differed from the other fat types with respect to its lower melting point (29.0 °C) and higher saponification (211.4 mg KOH/g) and iodine (50.55) values. The cattle fat types contained palmitic acid (16:0), stearic acid (18:0), oleic acid (18:1n‐9) and linoleic acid (18:2n‐6) as the major components of fatty acid composition (24.58–25.90%, 10.21–33.33%, 28.18–46.05%, 1.54–1.73%, respectively). A differential scanning calorimetry (DSC) study revealed that two characteristic peaks were detected in both crystallization and melting curves. Major peaks (T_peak) of tallow and intestinal fats were similar and determined as 24.10–27.71 °C and 2.16–4.75 °C, respectively, for crystallization peaks and 7.09–9.39 °C and 43.28–46.49 °C, respectively, for melting peaks in DSC curves; however, those of subcutaneous fat (12.48 °C and –6.79 °C for crystallization peaks and 3.56 °C and 23.55 °C for melting peaks) differed remarkably from those of the other fat types.     

Effect of repeated heating on thermal behavior of crude palm oil

Thermal behavior of crude palm oil (CPO) is important to determine the optimal fractionation process and product yield. In this study, the effects of repeated heating on thermal behavior of CPO were examined by differential scanning calorimetry. CPO was heated at 80°C for 5 min, and heating was repeated five times to simulate the common conditions experienced by an oil before reaching the refinery. The result revealed that the thermal behavior of CPO changed after heating. The change, however, occurred only in the behavior of the high-melting stearin peak but not in the low-melting olein peak. Overheating split the stearin peak at 17.30°C to two peaks at 18.88 and 17.30°C and formed a new peak at 11.28°C. Apparently, a new substance has been synthesized.     

Study on thermal behavior of impact polypropylene copolymer and its fractions

An impact polypropylene copolymer (IPC) was fractionated into three fractions using n‐octane as solvent by means of temperature‐gradient extraction fractionation. The glass transitions, melting, and crystallization behavior of these three fractions were studied by modulated differential scanning calorimeter (MDSC) and wide‐angle X‐ray diffraction (WAXD). In addition, successive self‐nucleation and annealing (SSA) technique was adopted to further examine the heterogeneity and the structure of its fractions. The results reveal that the 50°C fraction (F₅₀) mainly consists of ethylene‐propylene random copolymer and the molecular chains may contain a few of short but crystallizable propylene and/or ethylene unit sequences; moreover, the lamellae thicknesses of the resulting crystals are extremely low. Furthermore, 100°C fraction (F₁₀₀) mainly consist of some branched polyethylene and various ethylene‐propylene block copolymers in which some ethylene and propylene units also randomly arrange in certain segments, and some polypropylene segments can form crystals with various lamellae thickness. An obvious thermal fractionation effect for F₁₀₀ samples after being treated by SSA process is ascribed to the irregular and nonuniform arrangement of ethylene and propylene segments. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Insight into thermal,crystallization kinetics,and phase behaviors of palm kernel oil and its olein/stearin by differential scanning calorimetry

The fractionation of oils has received considerable research attention, aiming at the modification of the properties of oils. The thermal and crystallization properties of palm kernel oil (PKO) and its olein/stearin (PKOL/PKST) were systematically investigated using differential scanning calorimetry (DSC). Based on the isothermal DSC results, crystallization temperature exerted critical effect on co-crystallization of PKOL and PKST. Moreover, it is reported that PKOL could be further separated by controlling the crystallization temperature, while PKST is hard to be further separated. The PKOL/PKST mixtures with different compositions were prepared and subjected to dynamic DSC analysis. The results illustrated that PKO meets the phase equilibrium of quasi-solid solutions.     

Composition and crystallization of milk fat fractions

Milk fat was fractionated by solvent (acetone) fractionation and dry fractionation. Based on their fatty acid and acyl-carbon profiles, the fractions could be divided into three main groups: high-melting triglycerides (HMT), middle-melting triglycerides (MMT), and low-melting triglycerides (LMT). HMT fractions were enriched in long-chain fatty acids, and reduced in short-chain fatty acids and unsaturated fatty acids. The MMT fractions were enriched in long-chain fatty acids, and reduced in unsaturated fatty acids. The LMT fractions were reduced in long-chain fatty acids, and enriched in short-chain fatty acids and unsaturated fatty acids. Crystallization of these fractions was studied by differential scanning calorimetry and X-ray diffraction techniques. In this study, the stable crystal form appeared to be the β′-form for all fractions. At sufficiently low temperature (different for each fraction), the β′-form is preceded by crystallization in the metastable α-form. An important difference between the fractions is the rate of crystallization in the β′-form, which proceeds at a much lower rate for the lower-melting fat fractions than for the higher-melting fat fractions. This may be due to the much lower affinity for crystallization of the lower-melting fractions, due to the less favorable molecular geometry for packing in the β′-crystal lattice.     

A critical evaluation of thermal fractionation of butter oil

Butter was fractionated on the basis of temperature (17–29°C) without agitation using slow cooling of melted anhydrous fat in conjunction with gentle vaccum filtration to produce four solid and four liquid fractions. Each of the fractions was analyzed for fatty acid composition, triglyceride profile, and characterized by gel permeation high performance liquid chromatography and differential scanning calorimetry thermograms. Fatty acid analysis indicated that the solid fractions had slightly higher amounts of palmitic and stearic acid and lower levels of oleic acid, while the remaining analyses did not indicate any substantial compositional differences between the fractions. Although the 29°C solid fraction (∼10%) could be said to be somewhat unique, the natural variation in the normal seasonal composition of butterfat was almost equal to that obtained by fractionation. The experimental physicochemical data obtained for the fractions in this study extend and verify previous work on butteroil fractionation, and indicate that thermal fractionation has marginal merit. On the other hand, literature describing more positive thermal butteroil fractionation results obtained by the properietary Tirtiaux process (Fleurus, Belgium), indictes that it may be a more expedient avenue to explore and let market forces determine whether fractionation has a future in Canada and North America.     

Prediction of the thermal conductivity of liquids and liquid mixtures including crude oil fractions

A new method based on the Effective Carbon Number is presented for the prediction of the thermal conductivity of liquids and liquid mixtures. The Effective Carbon Number for each substance of interest can be calculated from its thermal conductivity at a reduced temperature of 0.6. The thermal conductivities of isoalkanes, cycloalkanes, aro-matics, alkanes, carboxylic acids, ketones, esters and aldehydes over a range of temperatures were predicted using this method and the results were compared with experimental values. The thermal conductivities of defined mixtures were also predicted using a quadratic mixing rule for the Effective Carbon Number. Lastly, the thermal conductivities of undefined mixtures such as crude oil fractions were calculated by treating each fraction as a single pseudocompo-nent. In all cases studied, calculated results compared favorably with experimental values.     

Improving the cold flow properties of biodiesel from waste cooking oil by surfactants and detergent fractionation

The use of surfactants and detergent fractionation to improve the cold flow properties of biodiesel from waste cooking oil (BWCO) was investigated. The effect of five types of surfactants, including sugar esters (S270 and S1570), silicone oil (TSA 750S), polyglycerol ester (LOP-120DP) and diesel conditioner (DDA) on the reduction of the cold filter plugging point (CFPP) of the BWCO, was evaluated, with the greatest reduction to the CFPP of the BWCO (from −10 °C to −16 °C) being was achieved by the addition of 0.02 wt% of polyglycerol ester (LOP-120P). Detergent fractionation of the BWCO was performed by first mixing partially crystallized biodiesel with a chilled detergent (sodium dodecylsulfate) solution accompanied by an electrolyte (magnesium sulfate), and then separating the mixture by centrifugation to obtain the BWCO liquid. An orthogonal experimental design was utilized to investigate the effects of the various parameters on detergent fractionation. The optimal parameters, as obtained by range analysis, were as follows: detergent loading 0.3 wt%, electrolyte loading 1.0 wt%, and water loading 150 wt%. The CFFP of the liquid biodiesel from waste cooking oil (LBWCO) was −17 °C with a yield of 73.1% when the detergent fractionation was performed under these conditions. A limited number of biodiesel physical and chemical properties were analyzed before and after the addition of surfactants and detergent fractionation.     

Liquid Chromatographic fractionation of oil-sand and crude oil asphaltenes

Asphaltenes extracted from Alberta oil sands (Athabasca, Cold Lake, and Peace River) and crude oils (Taber South and Fenn-Big Valley) were fractionated by sequential elution solvent chromatography (SESC) involving 10 organic solvents on a silica column. Athabasca asphaltenes and SESC fractions were further studied by elemental analysis, i.r., u.v., and n.m.r. spectroscopy. Incomplete extraction of maltenes from the oil-sand bitumens increased the yields of the first two SESC fractions, the saturates and aromatics, of oil-sand asphaltenes relative to the crude oil asphaltenes. About 55 wt% of the asphaltenes elute in fractions 3–5. Two distinct molecular types are present in the asphaltenes; namely, lower functionality species with lower heteroatom content and the higher functionality species with higher heteroatom content. Compounds eluting in fractions 3–10 are predominantly polynuclear aromatics with alkyl substituants and probably bridged by cycloalkanes. The extent of bridging as well as the location, number and type of heteroatoms determines the fraction in which each compound appears. Complexity of compounds eluting increases with time: earlier fractions are composed of smaller-size polynuclear aromatic centers and contain heteroatoms in predominantly ring locations, whereas later fractions contain a larger proportion of complex species and more functional heteroatom groups.     

Thermal behavior of butterfat fractions and mixtures of tripalmitin and butterfat

The melting and crystallization behavior of blends of tripalmitin and butterfat were compared with that of butterfat fractions, which were prepared by dry fractionation and by solvent extraction. There were marked similarities in the behavior of the blends, the dry fractions and some solvent fractions. This similarity was not shared with the behavior of the hardest solvent fractions. The functionality or hard butterfat fractions seemed to derive from an enrichment in long-chain saturated triglycerides. Improved functionality could therefore be achieved equally well by blending or by fractionation. Blends of tripalmitin and butterfat could be used as model butterfat fractions, or as an alternative to butterfat fractions in some applications.     

Changes in triacylglycerol molecular species and thermal properties of blended and interesterified mixtures of coconut oil or palm oil with rice bran oil or sesame oil

Blended oils were prepared by mixing appropriate amounts of coconut oil (CNO) or palm oil (PO) with rice bran oil (RBO) or sesame oil (SESO) to get approximately equal proportions of saturated/monounsaturated/polyunsaturated fatty acids in the oil. These blended oils were subjected to interesterification reactions using lipase to randomize the fatty acid distribution on the glycerol molecule. The fatty acid compositions of the modified oils were evaluated by gas chromatography while changes in triacylglycerol molecular species were followed by HPLC. The triacylglycerol molecular species of the blended oils reflected those present in the parent oil. Interesterification of the blended oils resulted in the exchange of fatty acids within and between the triacylglycerol molecules, resulting in alterations in the existing triacylglycerol molecules. Emergence of new triacylglycerol molecular species following interesterification was also observed. The thermal profiles of the native, blended and interesterified oils were determined by differential scanning calorimetry. Thermal behaviour, melting and crystallization properties of the modified oils showed significant changes reflecting the changes in the triacylglycerol molecules present in the oil. Therefore, interesterification of oils introduces significant changes in the physical properties of oils, even though the overall fatty acid composition of blended and interesterified oils remains the same.     

DSC study on the melting properties of palm oil, sunflower oil, and palm kernel olein blends before and after chemical interesterification

Changes in DSC melting properties of palm oil (PO), sunflower oil (SFO), palm kernel olein (PKOo), and their belends in various ratios were studied by using a combination of blending, and chemical interesterification (CIE) techniques and determining total melting (ΔH _f ) and partial melting (ΔH _i°C ) enthalpies. Blending and CIE significantly modified the DSC melting properties of the PO/SFO/PKOo blends. PO and blends containing substantial amounts of PO and PKOo experienced an increase in their DSC ΔH _f and ΔH _i°C following CIE. The DSC ΔH _f and ΔH _i°C of PKOo, blends of PO/SFO at 1∶1 and 1∶3 ratios, and all blends of PKOo/SFO significantly decreased after CIE. The DSC ΔH _f and ΔH _i°C of SFO changed little following CIE. Randomization of FA distribution within and among TAG molecules of PO and PKOo led to modification in TAG composition of the PO/PKOo blends and improved miscibility between the two fats and consequently diminished the eutectic interaction that occurred between PO and PKOo.     

Crystallization and melting properties of extra virgin olive oil studied by synchrotron XRD and DSC

Crystallization and melting properties of triacylglycerols in extra virgin olive oil were studied by using synchrotron X‐ray diffraction (XRD) and differential scanning calorimetry (DSC). The phase transitions were monitored by cooling and heating the samples at 2°C/min from 60 to ?60°C and vice versa. Upon cooling, a first DSC endothermic peak was recorded at ?9.6°C followed by one at ?33.5°C. These thermal events were associated to the formation of two different structures: a triple‐chain length (3L) having a c parameter of about 58.38 Å and a quadruple chain length structure (4L) with a c parameter of about 89.99 Å, respectively. Both structures evidenced a cell packing arrangement ascribable to a β′ form. During heating, part of the metastable β′ crystals rearranged into the more thermodynamically stable β form. Then, upon further heating, the sequential melting of the two crystal structures was observed. The melting was completed at 10.7°C. Beside this interpretation of XRD data, a model considering a cell with a c parameter of about 170 Å and a hexagonal crystal system was proposed. Even if more research is needed to validate this approach, it allowed all XRD events recorded during the experiments to be described. See commentary by Chiavaro [p. 267–269], http://dx.doi.org/10.1002/ejlt.201200415     

蒽油馏分深加工工艺现状及研究进展

介绍了蒽油馏分深加工的2种工艺、蒽油精制分离提取精蒽、菲、咔唑工艺的现状及研究进展,阐述了蒽油馏分加氢生产轻质燃料油工艺研究进展、工艺原理、工艺流程等。对山西焦化集团有限公司未来建设蒽油深加工项目提出了建议。     

油剂处理对PAN原丝热性能的影响

通过热重和热质联用手段研究了氨改性聚硅氧烷油剂处理对PAN原丝热性能的影响。结果表明,油剂在纤维表面的附着可以提高原丝的开始分解温度,并且在300℃以后,对原丝热性能的影响开始明显化,它还使原丝分解产物的逸出产生延迟,并且浓度有所下降。这是由于油剂薄膜层的存在对原丝热解过程的传热和传质两方面均有阻碍作用引起的。     

柴油微乳液的制备及其性能研究

介绍了-10<'#>,0<'#>柴油微乳液的组成,确定了柴油、水、表面活性剂的质量配比,采用超声波处理为分散手段制备了微乳化柴油;并将-10<'#>柴油制备的微乳液与0<'#>柴油制备的微乳液作了对比;对制得的微乳化柴油的十六烷值、闪点、密度、黏度、粒径、凝点、热值、胶质质量浓度等理化性能指标进行了测定与分析对比;同时...     

铝箔轧制废油中基础油分离及性能的研究

采用减压蒸馏法对铝箔轧制废油中的基础油进行分离回收。截取馏程为150~160℃的减压馏分,得到酸值0.027 mg KOH/g、运动粘度2.35 mm2/s、退火性能Ⅱ级、闪点82℃和馏程宽度为220~253℃的再生油。使用GC/MS对废油和再生油的组成进行分析,对其的酸值、馏程、粘度、闪点和油膜强度等理化性能和使用性能进行测定,并结合工业上铝箔轧制油性能要求对测定结果进行综合评价。结果表明,窄馏分油的主要性能指标达到使用要求。