Separation of squalene from palm fatty acid distillate using adsorption chromatography

A method to separate squalene from palm fatty acid distillate (PFAD) using neutralization‐hydrolysis‐neutralization before employing adsorption column chromatography was developed. Extraneous matters, especially free fatty acids (83.8%) and acylglycerols (12.7%), were first neutralized and removed before being subjected to hydrolysis by using commercially available, immobilized Candida antartica lipase, at 65 °C for 8 h. Neutralization followed by hydrolysis and repeated neutralization successfully concentrated squalene from an initial amount of 3.76% to 27.5%. Oil extracted from neutralized‐hydrolyzed‐neutralized PFAD was then passed through a Diaion HP‐20 column using reverse‐phase adsorption chromatography. Squalene was desorbed by hexane, with a recovery of 93%.     

Quality of byproducts from chemical and physical refining of palm oil and other oils

Being byproducts, palm soapstock, palm acid oil and palm fatty acid distillates (PFAD) have a wide range of quality and composition. They also consist of many impurities and minor components. Due to development of refining techniques. PFAD have largely replaced palm acid oil, especially in the producing countries. Although both palm acid oil and PFAD can be used for making low-quality laundry soap directly, they are often subjected to further treatment. They have found many industrial applications, especially in the feed and fatty acid industries. Quality of recovered oil from spent earth can be as good as bulk of the bleached stock if proper solvent such as hexane is used for extraction. Spent earth can also be used for incineration to produce energy, cattlefeed and landfill.     

Covalorization of Palm Oil-Refining by-Products as Soaps

This study deals with the covalorization of spent bleaching clay (SBC) and palm fatty acid distillate (PFAD), the by-products of palm oil-refining plants (3 Mt. year⁻¹), through soap manufacture. Obtained SBC and PFAD samples show differing acidity and saponification values depending on their content of free fatty acids and of acylglycerols. The SBC sample had an acidity of 60.5% and a saponification value of 182 mg KOH g⁻¹ of oil, and the PFAD sample has an acidity of 88.4% and a saponification value of 204 mg KOH g⁻¹ of oil. Soaps are prepared using the stoichiometric amount of NaOH, under varying proportion of water introduced through the basic solution. The overall reaction (neutralization and saponification) is complete (99.9%) with PFAD, whereas the yield reaches only 56.1% with SBC. When mixing SBC and PFAD, for example under a 1:1 weight ratio, the overall reaction completion (87.7%) is surprisingly higher than expected based on the computed individual reaction yields (78%), showing a synergistic effect of about 10% on the course of the saponification reaction of acylglycerols in SBC. The water content was found to be a critical parameter, 30% w/w of added water providing the highest yield. These results show an innovative way for covalorizing two important by-products of palm oil industrial processing as a single final product. By-products of the physical refining of other oils could also be valorized following the same method.     

Synthesis and Application of Palm Fatty Acid Distillate Based Alkyd Resin in Liquid Detergent

Palm fatty acid distillate (PFAD) is the by-product obtained during physical refining of crude palm oil, which mainly consists of free fatty acids along with minor amounts of glycerides, bioactive compounds such as tocopherols, tocotrienols, phytosterols, squalene, other hydrocarbons. In the present work, an eco-friendly alkyd resin was prepared using sustainable feedstock such as PFAD along with rosin. The various physico-chemical properties of PFAD-based alkyd resin (PFAD-AR) such as acid value, saponification value, viscosity and volatile matter were determined and compared to palm oil based alkyd resin (PO-AR). The structural properties of the alkyd resins were investigated using Fourier transform infrared (FTIR) and proton nuclear magnetic resonance (¹H NMR) spectroscopic techniques. The study presents the utilization of PFAD-based alkyd resin with sodium lauryl sulfate (SLS) and sodium lauryl ether sulfate (SLES) in the liquid detergent formulation. The performance properties of the PFAD-based alkyd resin liquid detergent formulations such as surface tension, wetting power and detergency were comparable with palm oil based alkyd resin liquid detergent formulations and with commercial liquid detergent (CLD). Surface tensions of liquid detergent formulations varied from 20 to 30 mN/m with decrease in concentration. The foaming properties of alkyd resin based liquid detergents are reduced with the increase in the amount of alkyd resin polymer in the formulations. Therefore, it has potential application as a foam reducer in detergent for washing machines.     

Noncarotenoid hydrocarbons in palm oil and palm fatty acid distillate

Column chromatographic and gas chromatographic-mass spectroscopic (GCMS) analyses for minor and trace noncarotenoid hydrocarbons of crude palm oil and palm fatty acid distillate revealed the presence of a wide range of n-alkanes (C₁₂H₂₆ to C₃₆H₇₄) and n-alkenes in addition to the major component, squalene. Hydrocarbon components concentrated in palm fatty acid distillate where squalene was dominant, but degradation products such as alkenes (from fatty acids or glycerides), aromatic hydrocarbons (from carotenes) and diterpene hydrocarbons (from tocotrienols) were detected in significant quantities, superseding the naturally occurring n-alkanes. Mechanisms proposed suggest that degradation of the valuable vitamin E or tocotrienols needs to be minimized in physical refining.     

Esterification of Palm Fatty Acid Distillate Using a Sulfonated Mesoporous CuO‐ZnO Mixed Metal Oxide Catalyst

A nanocrystalline mesoporous CuO‐ZnO hollow sphere was successfully fabricated by the hydrothermal method. The nanocomposite was formed in the presence of polyethylene glycol as a dispersant and D‐glucose as a template. The mesoporous CuO‐ZnO catalyst was further functionalized with benzenesulfonic acid to catalyze the esterification of palm fatty acid distillate (PFAD). The physicochemical, textural, structural, and thermal properties of the mesoporous CuO‐ZnO mixed‐oxide catalysts were evaluated. The modified mesoporous catalyst possessed unique textural properties. With a Cu/Zn atomic ratio of 1.0 the best catalytic activity through PFAD esterification was achieved. The optimum reaction conditions in terms of methanol/PFAD molar ratio, catalyst concentration, reaction temperature, and reaction time were determined.     

Sulfonated Beet Pulp as Solid Catalyst in One-Step Esterification of Industrial Palm Fatty Acid Distillate

In this research a new heterogeneous catalyst has been prepared for biodiesel production. The catalyst was prepared by sulfonating industrial sugar waste. Unlike homogeneous catalysts, which require further purification and separation from the biodiesel production reaction media, this inexpensive synthetic catalyst does not need to go through an additional separation process. This advantage consequently minimizes the total application costs. The catalyst was prepared by partially carbonizing sugar beet pulp at 400 °C. The carbonization product was then sulfonated with concentrated H₂SO₄ vapor in order to produce a solid catalyst. The prepared catalyst was used in the esterification reaction between palm fatty acid distillate (PFAD) and methanol. The effects of the temperature, methanol/PFAD ratio, reaction time and catalyst dosage on the efficiency of the production were individually investigated. The optimum biodiesel production occurred at 85 °C, a reaction time of 300 min, catalyst dosage of 3 g and methanol/PFAD ratio of 5:1 (mol/mol), lowering the acid value from 198 to 13.1 (mg KOH/g oil) or the equivalent, with a fatty acid methyl ester yield of around 92 %. The results suggest that the synthesized inexpensive catalyst is useful for biodiesel production from PFAD.     

Esterification of palm fatty acid distillate (PFAD) in supercritical methanol: Effect of hydrolysis on reaction reactivity

This study demonstrated the potential use of local palm fatty acid distillate (PFAD) as alternative feedstock for fatty acid methyl esters (FAMEs) production and the possibility to replace the conventional acid-catalyzed esterification process (with H₂SO₄), which was industrially proven to suffer by several corrosion and environmental problems, with non-catalytic process in supercritical methanol. At 300 °C with the PFAD to methanol molar ratio of 1:6 and the reaction time of 30 min, the esterification of PFAD in supercritical methanol gave FAMEs production yield of 95%. Compared with transesterification of purified palm oil (PPO) in supercritical methanol, the production of FAMEs reached the maximum yield of only 80% at 300 °C with higher requirement for methanol (1:45 PPO to methanol molar ratio). Compared with the conventional acid-catalyzed esterification of PFAD, only 75% FAMEs yield was obtained in 5 h. The presence of water in the feed (between 0 and 30% v/v) was found to lower the yield of FAMEs production from PFAD significantly. This negative effect was proven to be due to the further hydrolysis of FAMEs, which nevertheless can be minimized when high content of methanol was used.     

Dry Fractionation Approach in Concentrating Tocopherols and Tocotrienols from Palm Fatty Acid Distillate: A Green Pretreatment Process for Vitamin E Extraction

Palm fatty acid distillate (PFAD) is a rich source of vitamin E. As compared to other vegetable oil, PFAD has higher tocotrienol (70–80%) over tocopherol content, which makes it a valuable source for vitamin E extraction. Current vitamin E extraction methods are not sustainable due to the intensive usage of chemical and high operational cost. Hence, the present study investigated for the first time using dry fractionation process as a green and economical pretreatment method for separating solid fraction (stearin) and liquid fraction (olein) in order to concentrate vitamin E from PFAD in olein fraction. We examined the dry fractionation conditions: crystallization ending temperature (36–44 °C), cooling rate (0.3 and 1.5°C min⁻¹), stirring speed (20–125 rpm), and holding time (0–60 min) on the composition of unsaturated and saturated fatty acids as well as vitamin E content in liquid fraction (olein) and solid fraction (stearin) using gas chromatography and high performance liquid chromatography, respectively. In most of these conditions, vitamin E was ultimately higher in olein fraction as compared to stearin fraction, which is correlated with the high degree of unsaturation. Under a cooling rate of 0.3°C min⁻¹, 90 rpm stirring speed, and ending crystallization of 38 °C, the highest vitamin E rich olein fraction was attained with 1479 ± 10.51 ppm in 50 g olein fraction as compared to 1366 ± 7.94 ppm in 500 g of unfractionated PFAD.     

Use of Oxone® as a Potential Catalyst in Biodiesel Production from Palm Fatty Acid Distillate (PFAD)

Catalysis Letters - Palm fatty acid distillate PFAD is an example of potential low-cost palm biofuel second generation feedstock, most used as a source of fatty acid for non-food applications in...     

Production of biodiesel from palm fatty acid distillate using sulfonated-glucose solid acid catalyst:Characterization and optimization

A palm fatty acid distillate (PFAD) has been used for biodiesel production. An efficient sulfonated-glucose acid catalyst (SGAC) was prepared by sulfonation to catalyze the esterification reaction. The effect of three variables i.e. methanol-to-PFAD molar ratio, catalyst amount and reaction time, on the yield of PFAD esters was studied by the response surface methodology (RSM). The optimum reaction conditions were:12.2:1 methanol-to-PFAD molar ratio, 2.9%catalyst concentration and 134 min of time as predicted by the RSM. The reaction under the optimum conditions resulted in 94.5%of the free fatty acid (FFA) conversion with 92.4%of the FAME yield. The properties of the PFAD esters were determined according to biodiesel standards.     

Characteristics of coal upgraded with heavy oils

We investigated the ability of an oil coating to upgrade Indonesian low-rank coal, which has a low ash content and a moisture content of approximately 30%. Proximate and ultimate analyses of the characteristics of coal samples containing different amounts of asphalt (ASP) and palm fatty acid distillate (PFAD) were studied, including the samples’ calorific values, crossing-point temperatures (CPT), specific surface areas, pore sizes, structural changes, and moisture readsorption. The results showed that the 0.5% PFAD-coated coal was the highest quality. This coal showed few physical and chemical changes, and it had a low surface area and a high CPT value.     

Cleaner production technologies for the palm oil industry

This paper discusses some potential cleaner production technologies for the palm oil industry. These include supercritical fluid extraction, short path distillation and membrane separation. Over the last two decades, palm oil and minor components especially phytonutrients such as carotenoids, tocols (tocopherols and tocotrienols), sterols, squalene and phospholipids have received much attention for their nutritional properties. The recovery of these phytonutrients is a challenging task because (i) some of them (e. g. carotenoids and vitamin E) are sensitive to heat, light and air; (ii) they are of different polarity, from non‐polar (e. g. squalene) to relatively polar (e. g. phospholipids) and (iii) they are of differing molecular weights. Suitable technologies are needed to recover all these phytonutrients without damage. The paper discusses the latest development of these technologies.     

Extraction of α‐tocopherolquinone from vegetable oil deodorizer distillate waste

In industry, deodorizer distillate waste is one of the last products of refined edible oil after the removal of commercially important value components such as fatty acids, sterols, squalene, and vitamin E. The refinery process itself is the cause of a significant amount of loss in vitamin E due to distillation and thermal oxidation. The distillate waste has a very limited commercial value, therefore requires additional costs for a safe environmental disposal. One of the main vitamin E oxidation products found in large quantities in oil waste is tocopherolquinone (TQ). A literature search has revealed that in the past several techniques including a variety of solvent extractions, saponification, or column extraction have been used for TQ isolation with limited success. The present study is a new cost‐effective liquid–liquid extraction method developed to isolate α‐TQ from vegetable oil steam distillate or distillate waste. High recovery results ranging from 31 to 120% were obtained depending on the ratio between the sample and three different organic extraction solvents (acetonitrile, methanol, and hexane) combined.     

Carbohydrate-derived Solid Acid Catalysts for Biodiesel Production from Low-Cost Feedstocks: A Review

Currently, most biodiesels are produced from virgin vegetable oils using a transesterification reaction. However, there are a number of other potential cheap sources for biodiesels, such as deep-frying oils/fats and palm fatty acid distillate (PFAD). PFAD is a lower-value by-product of the palm oil industry and is an economical source for biodiesel production. Due to the high cost of biodiesel production, the formulation of a new method to produce a cheaper biodiesel is imperative. Low-quality feedstocks (especially PFAD) using green and highly reusable catalysts have gained popularity due to their low production cost. High free fatty acids (HFFA) in the feedstock causes problems during the biodiesel production process, especially with the use of basic heterogeneous and homogenous catalysts. Recently, the effectiveness of a solid acid catalyst to catalyze biodiesel production from HFFA feedstock has caught the attention of researchers.

This comprehensive article explores the use of low-quality feedstocks and carbon-based catalysts for the conversion of a waste refinery crude palm oil product which contains a high percentage of FFA. The production and characterization of carbohydrate-derived solid acid catalysts are discussed, including their physico-chemical property measurements. Techniques used for the synthesis of biodiesels are also included. In addition, transesterification process variables such as the oil/methanol molar ratio, catalyst concentration, reaction time, and temperature are investigated. The final part of the article contains the combustion, emissions, and performance of produced biodiesels. Finally, conclusions, including perspectives and future developments, are also presented. The aim of this article is to demonstrate the current state of the use of low-quality feedstocks and green heterogeneous solid acid catalysts for the use in biodiesel production.     

Separation of squalene from olive oil deodorizer distillate using supercritical fluids

In this study, an integrated strategy using supercritical fluids for extraction of squalene from olive oil deodorizer distillate (OODD), one of the most important by‐products of the olive oil refining process is presented. First, OODD was esterified in supercritical methanol, and then squalene was extracted from the sample consisting of 66% methyl ester using supercritical CO₂. The extraction conditions, i.e., pressure (88.2–121.8 bar), temperature (41.6–58.4°C) and extraction time (129.6–230.4 min), were optimized via RSM to achieve the highest squalene content. The optimal results were obtained at a temperature of 52.05°C, pressure of 104.8 bar and extraction time of 180 min. Consequently, two kinds of value‐added products such as biodiesel (up to 96% FAME, in extract) and olive squalene (up to 75%, in raffinate) were produced in shorter processing times when compared with distillation results of 70 h. Practical applications: Traditionally, squalene is extracted from liver oil of rare deep‐sea sharks. Here we present the recovery of vegetal squalene in high purity from OODD. Our approach also presents a simple, reliable, and mobile solution. Squalene is widely used in cosmetics as a protective agent and natural moisturizer and as an adjuvant in influenza vaccines.     

Recovered oil from palm-pressed fiber: A good source of natural carotenoids,vitamin E,and sterols

Recovered fiber from pressed palm fruits, which is normally burned as fuel to provide energy for the palm oil mills, has now been found to be a rich source of carotenoids, vitamin E (tocopherol and tocotrienols), and sterols. Residual oil (5–6% on dry basis) extracted from palm press fibers contains a significant quantity of carotenoids (4000–6000 ppm), vitamin E (2400–3500 ppm), and sterols (4500–8500 ppm). The major identified carotenoids are α-carotene (19.5%), β-carotene (31.0%), lycopene (14.1%), and phytoene (11.9%). In terms of vitamin E, α-tocopherol constitutes about 61% of the total vitamin E present, the rest being tocotrienols (α-, γ-, and δ-). The major sterols present are β-sitosterol (47%), campesterol (24%), and stigmasterol (15%). The oil extracted from palm-pressed fiber is contaminated with about 30% of palm kernel oil. The quality of this fiber oil is slightly lower than that of crude palm oil in terms of the content of free fatty acids, peroxide value, and anisidine value.     

Phytonutrient content and oil quality of selected edible oils upon twelve months storage

Edible oils contain naturally occurring phytonutrients and therefore exhibit numerous beneficial health effects. However, the phytonutrients tend to degrade in different extent with storage duration and temperature. In this study, the impact of storage conditions on the stability of phytonutrients, including vitamin E, carotenoid, phytosterols and squalene, and oil quality, including free fatty acids (FFA), peroxide value (PV), anisidine value (AV), and oxidative stability index (OSI) of red palm-pressed mesocarp olein, palm olein, extra virgin olive oil, and sunflower oil were investigated. The oils were stored in three conditions, 23°C (with light and without light) and 35°C (without light). Results showed that the retention percentages of phytonutrients where in the range of 0%–100% for vitamin E, 51.24%–83.63% for carotenoid, 83.40%–100% for phytosterols and 27.94%–100% for squalene. Pearson correlation analysis between phytonutrients and oil quality of oils in different storage conditions showed that correlation coefficient values (r) were in the range of −1 to 0 for FFA, −1 to 0.22 for PV, −1 to 0.33 for AV, and −0.23 to 1 for OSI, implying that correlations between both variables are not in same direction. Degradation studies of phytonutrients using zero-order kinetic model where optimum-case conditions exhibited highest half-life (t_1/2) among the three conditions. In conclusion, storage conditions and synergistic effect affected the phytonutrients stability in the oils and oil quality in different extent. In general, storage at ambient temperature and dark condition contributed to the best phytonutrients retention and oil quality.     

Application of supercritical fluid chromatography in the quantitative analysis of minor components (carotenes,vitamin E,sterols, and squalene) from palm oil

The application of supercritical fluid chromatography (SFC) coupled with a UV variable-wavelength detector to isolate the minor components (carotenes, vitamin E, sterols, and squalene) in crude palm oil (CPO) and the residual oil from palm-pressed fiber is reported. SFC is a good technique for the isolation and analysis of these compounds from the sources mentioned. The carotenes, vitamin E, sterols, and squalene were isolated in less than 20 min. The individual vitamin E isomers present in palm oil were also isolated into their respective components, α-tocopherol, α-tocotrienol, γ-tocopherol, γ-tocotrienol, and δ-tocotrienol. Calibration of all the minor components of palm as well as the individual components of palm vitamin E was carried out and was found to be comparable to those analyzed by other established analytical methods.     

Crude Palm Oil from Interspecific Hybrid Elaeis oleifera × E. guineensis: Alcoholic Constituents of Unsaponifiable Matter

Interspecific hybrid Elaeis oleifera × E. guineensis (O×G) palm is currently receiving increasing attention because of its interesting glycerides structure and composition. In this study, the alcoholic constituents of unsaponifiable matter of crude hybrid O×G palm oil were characterized for the first time and compared to data obtained analyzing crude African palm oil (E. guineensis).Total unsaponifiable matter content was 1.18 ± 0.11 g/100 g in O×G hybrid oil and 1.05 ± 0.06 g/100 g in African palm oil. O×G oil was characterized by lower contents of squalene and alcoholic constituents where the main differences concerned 4‐desmethylsterols and isoprenoid alcohols: O×G oil was characterized by higher (23.6 ± 6.1 %) contents of isoprenoid alcohols and by a different phytol/geranylgeraniol ratio. The tocol fraction constituted the class of unsaponifiable components on which the genetic exerts the greatest influence: tocol content showed no significant differences between the two oils, however, hybrid palm oil was characterized by higher percentages of γ‐tocotrienol (59.7 ± 1.1) and δ‐tocotrienol (11.7 ± 0.8) and lower percentages of tocopherols (10.6 ± 0.3), almost entirely constituted of the α isomer. These results suggest that O×G oil can also be considered an interesting alimentary source of nutraceutical components, especially for bioactive tocotrienols.