Synthesis of economically viable biodiesel from waste frying oils (WFO)

In present communication, waste frying oil (WFO) has been used as a feedstock for biodiesel synthesis. WFO, procured from a local Indian restaurant possessed an acid value of 0.84 mg KOH/g, which is low enough for single step transesterification reaction. Biodiesel (fatty acid methyl esters) was washed after transesterification reaction and the yield got lowered substantially (from 96% to 86.36%) after water washing owing to loss of esters. 30:100 vol% (methanol to oil), 0.6 wt% NaOCH₃, 60°C temperature and 600 rpm agitation in 1 h reaction time was found to be optimum for transesterification reaction. ¹H NMR spectrum showed a high conversion (95.19%) of fatty acids in WFO to biodiesel in 2 h reaction time. Almost complete conversion (99.68%) was attained in 2 h reaction time. © 2011 Canadian Society for Chemical Engineering     

Biodiesel production from waste frying oil in sub- and supercritical methanol on a zeolite Y solid acid catalyst

Waste frying oil (WFO) is a very important feedstock for obtaining biodiesel at low cost and using WFO in transesterification reactions to produce biodiesel helps eliminate local environmental problems. In this study biodiesel was produced from WFO in sub- and super-critical methanol on a zeolite Y solid acid catalyst. The procedure was optimized using a design of experiments by varying the methanol to WFO molar ratio, the reaction temperature, and the amount of catalyst. Typical biodiesel yields varied from 83 to nearly 100% with methyl esters content ranging from 1.41–1.66 mol·L^-1 and typical dynamic viscosities of 22.1-8.2 cP. Gas chromatography was used to determine the molecular composition of the biodiesel. The reaction products contained over 82 wt-% methyl esters, 4.2 wt-% free acids, 13.5 wt-% monoglycerides, and 0.3 wt-% diglycerides. The transesterification of WFO with methanol around its critical temperature combined with a zeolite Y as an acid catalyst is an efficient approach for the production of biodiesel with acceptable yields.     

Application of Multivariate Analysis in Mid-Infrared Spectroscopy as a Tool for the Evaluation of Waste Frying Oil Blends

Mid-infrared spectroscopy, in association with multivariate chemometric techniques, was employed for pattern recognition and the determination of the composition of waste frying oils (WFO); data are presented in terms of the percentage of soybean oil, palm oil and hydrogenated vegetable fat in frying oil blends. Principal component analysis (PCA) was performed using spectral data (3,000–600 cm⁻¹) to discriminate between the samples containing 100% soybean oil, 100% palm oil, 100% hydrogenated vegetable fat groups and their blends. Additionally, the results indicated that partial least squares (PLS) models based on mid-infrared spectra were suitable as practical analytical methods for predicting the oil contents in WFO blends. PLS models were validated by a representative prediction set, and the root mean square errors of prediction (RMSEP) were 2.8, 4.7 and 5.5% for palm oil, soybean oil and hydrogenated vegetable fat, respectively. The proposed methodology can be very useful for the rapid and low cost determination of waste frying oil composition while also aiding in decisions regarding the management of oil pretreatment and production routes for biodiesel production.     

Biodiesel Production from Soybean Oil Catalyzed by Li<Subscript>2</Subscript>CO<Subscript>3</Subscript>

In the present study, we synthesized biodiesel from soybean oil through a transesterification reaction catalyzed by lithium carbonate. Under the optimal reaction conditions of methanol/oil molar ratio 32:1, 12 % (wt/wt oil) catalyst amount, and a reaction temperature of 65 °C for 2 h, there was a 97.2 % conversion to biodiesel from soybean oil. The present study also evaluated the effects of methanol/oil ratio, catalyst amount, and reaction time on conversion. The catalytic activity of solid base catalysts was insensitive to exposure to air prior to use in the transesterification reaction. Results from ICP-OES exhibited non-significant leaching of the Li₂CO₃ active species into the reaction medium, and reusability of the catalyst was tested successfully in ten subsequent cycles. Free fatty acid in the feedstock for biodiesel production should not be higher than 0.12 % to afford a product that passes the EN biodiesel standard. Product quality, ester content, free glycerol, total glycerol, density, flash point, sulfur content, kinematic viscosity, copper corrosion, cetane number, iodine value, and acid value fulfilled ASTM and EN standards. Commercially available Li₂CO₃ is suitable for direct use in biodiesel production without further drying or thermal pretreatment, avoiding the usual solid catalyst need for activation at high temperature.     

Palm olein quality parameter changes during industrial production of potato chips

New legislation introduced in South Africa for the quality of used frying oils has resulted in the need to identify quicker, more suitable methods that correlate well with results from two official methods, namely, total polymerized glycerides and total polar components. Oil and product samples were taken at regular intervals during a commercial frying process in palm olein. Oil samples were analyzed for a number of different quality parameters viz. tocopherol content, dielectric constant, total polymerized glycerides, total polar components, tertiary butylhydroquinone (TBHQ) content, anisidine value, Rancimat induction period, and free fatty acid content, and the results statistically compared to results from official methods. Oil was expressed from product stored under accelerated conditions and analyzed for the same quality parameters. Fried product was also subjected to sensory evaluation to measure the degree of oil deterioration and sensory preference. The frying trial was successfully executed with refined, bleached, and deodorized palm olein and the frying oil used to a free fatty acid (FFA) content of 0.41%. Oil and product sampling were done at different FFA value levels. Frying oil quality was verified at the onset of the trial and at regular intervals. The frying oil total polar component value increased to approximately half of the limit set by the official regulation. This point was reached mainly due to the high starting value of the fresh oil. Frying oil total polymerized glycerides increased from below 1% to 2.1%. This increase is negligible when compared to the general trend for polyunsaturated oils. The alternative laboratory methods used for predicting oil quality can be rated as follows: total tocopherol content >dielectric constant >FFA >TBHQ content >anisidine value >Rancimat induction period. The first three methods correlated well with total polar component levels and it is recommended that the dielectric constant and FFA measurements be applied for monitoring oil condition during frying. It is possible that viscosity changes could be used for the monitoring of polyunsaturated frying oils. Evaluation of oil extracted from product revealed a negligible effect of non-oil components on oil quality parameters. The same was observed when product was stored at −10°C and at 37°C.     

Production of Isopropyl and Methyl Esters from Yellow Mustard Oil/IPA Miscellas

Using an isopropyl alcohol (IPA):flour [volume:weight (ml:g)] ratio of 1.5:1 per stage of extraction resulted in an oil yield of 86.3%. The combined miscella (IPA + oil), which contained 90.6 wt% IPA, 9.8 wt% oil, and 2.1 wt% water, was used as a feedstock for biodiesel production by transesterification. Transesterification of the IPA/oil miscella dehydrated using adsorption on 4Å molecular sieves with 1.2 wt% (based on oil) potassium hydroxide for 2 h at 72 °C converted only 29% of the feed to esters. The addition of methanol (MeOH) resulted in an ester yield of 87%, consisting of 79% methyl ester and 7% isopropyl ester when starting with an IPA:oil:MeOH molar ratio of 146:1:30. By increasing the KOH catalyst to 3 wt%, the ester yield increased to 94%. To increase the ester yield, the miscella was pretreated with sulfuric acid. This resulted in a reduction of the IPA content, the removal of other impurities such as phospholipids, and reduction of the water mass fraction to less than 1%. When IPA was used as a cosolvent with methanol in the transesterification process, a very high ester conversion (>99%) was achieved. The biodiesel produced was compliant with ASTM standards, showing that IPA can be used as a solvent for oil extraction from yellow mustard flour.     

Effect of low temperature on the microwave-assisted vacuum frying of potato chips

The objective of this study was to investigate the effect of low temperature on the microwave-assisted vacuum frying of potato chips. A newly built, in-house, microwave-assisted frying machine was developed and used in this study. The effect of low temperature on the microwave-assisted vacuum frying of potato chips was investigated via comparing sample properties prepared with frying temperatures of 90°C, 95°C, and 100°C. The experience was taken at the same vacuum degree in every frying process. Parameters of included moisture content, oil content, color parameters (lightness, redness, and yellowness), and textures (hardness, crispness) were used to evaluate the effect of different frying temperatures on the microwave-assisted vacuum frying of potato chips. Results showed that with lower temperature in microwave-assisted frying, the rate of moisture evaporation of potato chips was slowed down and the time of the ending of frying was prolonged from 10 min with a frying temperature of 100°C to 14 min with 90°C and 12 min with 95°C. Meanwhile, the oil content in fried potato chips was increased with lower temperature in microwave-assisted vacuum frying. The breaking force of final products are not significantly (p > 0.05) affected in different frying temperatures of microwave-assisted vacuum frying. Also, the frying temperature of 100°C in microwave-assisted vacuum frying had better preservation of natural color than the lower frying temperature with prolonged frying time. Results showed that the temperature is one of the main factors that affect the quality of microwave-assisted vacuum frying of potato chips and the producer could find suitable temperature conditions according to experience.     

Rice husk ash as an adsorbent for purifying biodiesel from waste frying oil

The goal of this work is to study the purification of biodiesel from waste frying oil (WFO) using rice husk ash (RHA) at concentrations of 1%, 2%, 3%, 4% and 5% (w/w) and compare it with two other different purification methods, the traditional acid solution (1% aqueous H₃PO₄) and with the commercial adsorbent Magnesol® 1% (w/w). The structure and composition of the RHA were studied to better understand its properties as an adsorbent. In a concentration of 4%, the RHA showed excellent results for removal impurities from biodiesel. The high concentration of silica in its composition and the presence of meso and macropores can explain its high capacity of adsorption. Thus, the RHA, that is a byproduct of the rice processing, can appear as an alternative material for biodiesel purification.     

Biodiesel production using tetramethyl- and benzyltrimethyl ammonium hydroxides as strong base catalysts

In recent years, the acceptance of fatty acid methyl esters (biodiesel) as an alternative fuel has rapidly grown in EU. The most common method for biodiesel production is based on triglyceride transesterification to methyl esters with dissolved sodium hydroxide in methanol as catalyst. In this study, cottonseed oil and used frying oil were subjected to the transesterification reaction with tetramethyl ammonium hydroxide and benzyltrimethyl ammonium hydroxide as strong base catalysts. This work investigates the optimum conditions for biodiesel production using amine-based liquid catalysts. Biodiesel ester content was strongly related with the type of feedstock and the reaction variables, such as those of the catalyst concentration, methanol to oil molar ratio, and reaction time. The overall results suggested that the transesterification of cottonseed oil achieved high conversion rates with both catalysts, while the use of waste oil resulted in lower yields of methyl esters due to the possible formation of amides.     

Analysis of parameters and interaction between parameters of the microwave-assisted continuous transesterification process of Jatropha oil using response surface methodology

A simple continuous process was designed for the transesterification of Jatropha curcas (J. curcas) oil to alkyl esters using microwave-assisted method. The product with purity above 96.5% of alkyl ester is called the biodiesel fuel. Using response surface methodology, a series of experiments with three reaction factors at three levels were carried out to investigate the transesterification reaction in a microwave and conversion of alkyl ester from J. curcas oil with NaOH as the catalyst. The results showed that the ratio of methanol to oil, amount of catalyst and flow rate have significant effects on the transesterification and conversion of alkyl ester. Based on the response surface methodology using the selected operating conditions, the optimal ratio of methanol to oil, amount of catalyst and flow rate of transesterification process were 10.74, 1.26 wt% and 1.62 mL/min, respectively. The largest predicted and experimental conversions of alkyl esters (biodiesel) under the optimal conditions are 99.63% and 99.36%, respectively. Our findings confirmed the successful development of a two-step process for the transesterification reaction of Jatropha oil by microwave-assisted heating, which is effective and time-saving for alkyl ester production.     

Accumulation of 5-Hydroxymethylfurfural in Oil During Frying of Model Dough

5-Hydroxymethylfurfural (HMF), a thermal process contaminant, forms in food during frying as a result of the Maillard reaction and caramelization. Owing to its chemical properties, HMF formed in foods during frying partially transfers into frying oil. This study aimed to investigate the accumulation of HMF in oil during repetitive frying operations. A model dough composed of 25 % of glucose was fried at 160, 170, 180 °C for 50 frying cycles. Apart from total polar compounds (TPC), accumulation of HMF was determined in oils during repetitive frying operations. Increasing frying temperature also increased the amount of HMF formed in dough, and those transferred to oil. Prolonging frying cycles to 150, increasing amount of dough being fried to 100 g and frying time to 10 min caused the TPC content to reach 25 % at the 130th frying cycle at 180 °C. Under the same frying conditions, the concentration of HMF showed a rapid increase at the first 10th frying cycle. Its increase was at a slower rate until the 50th frying cycle reaching a plateau level exceeding 5.0 mg/L. The results revealed that HMF transferred and accumulated in the frying oil during repetitive frying. The HMF concentration exceeding 5.0 mg/L in oil may be considered as an indicator for heavily used frying oil. Correlation between TPC and HMF contents of frying oil showed no linear correlation.     

Comparison of the Frying Performance of High Oleic Oils Subjected to Discontinuous and Prolonged Thermal Treatment

Frying is a popular practice because of its unique sensory characteristics and low cost. The high temperature reached with this cooking method alters molecules present in the oil. The deterioration of the oil depends primarily on its chemical composition. The aim of this study was to evaluate the thermal stability of high oleic sunflower oil (HOSO), sunflower oil (SO) and mixed oil (MIX) during deep frying of French fries. Octanoic acid and unsaturated fatty acid (UFA)/saturated fatty acid (SFA) ratio showed a good correlation with total polar compounds (TPC) for all frying samples analyzed. HOSO and MIX were characterized by reduced levels of thermal degradation, while SO resulted in the highest values of oxidation products (highest TPC values). SO was also the oil more retained by the food matrix, whereas MIX was the least absorbed. HOSO and MIX, having a high oleic acid content (77.58 and 59.92 %, respectively) and a low linoleic acid content (13.42 and 25.70 %, respectively), showed the best characteristics for the frying process.     

Evaluation of Siberian Apricot (<Emphasis Type="Italic">Prunus sibirica</Emphasis> L.) Germplasm Variability for Biodiesel Properties

The potential for using Siberian apricot (Prunus sibirica L.) seed kernel oil as a source of biodiesel raw material is often overlooked when considering Siberian apricots as a greening tree in China. The aim of this research was to study and compare the oil content and fatty acid composition of 17 germplasm accessions in northern regions of China. Oil content ranged from 44.73 to 57.83 % with a mean of 50.18 % for the 17 accessions. In AS-080, AS-013, AS-017 and AS-027, oil contents were higher than 55 %. Percentages of fatty acids varied greatly among different accessions, but all the accessions contained high amounts of important oleic acid. The biodiesel properties of the Siberian apricot seed kernels oil methyl ester were determined and compared to the relevant specifications from the ASTM D6751-2003, EN 14214-2005 and GB/T 20828-2007. In general, germplasm accession PS-80 has been identified as the ideal feedstock for biodiesel production while germplasm accessions PS-17 and PS-27 were found to be the promising feedstock for biodiesel production.     

Development and Scale-up of Aqueous Surfactant-Assisted Extraction of Canola Oil for Use as Biodiesel Feedstock

Aqueous surfactant-assisted extraction (ASE) has been proposed as an alternative to n-hexane for extraction of vegetable oil; however, the use of inexpensive surfactants such as sodium dodecyl sulfate (SDS) and the effect of ASE on the quality of biodiesel from the oil are not well understood. Therefore, the effects on total oil extraction efficiency of surfactant concentration, extraction time, oilseed to liquid ratio and other parameters were evaluated using ASE with ground canola and SDS in aqueous solution. The highest total oil extraction efficiency was 80 %, and was achieved using 0.02 M SDS at 20 °C, solid–liquid ratio 1:10 (g:mL), 1,000 rpm stirring speed and 45 min contact time. Applying triple extraction with three stages reduced the amount of SDS solution needed by 50 %. The ASE method was scaled up to extract 300 g of ground canola using the best combination of extraction conditions as described above. The extracted oil from the scale-up of the ASE method passed the recommendation for biodiesel feedstock quality with respect to water content, acid value and phosphorous content. Water content, kinematic viscosity, acid value and oxidative stability index of ASE biodiesel were within the ASTM D6751 biodiesel standards.     

Microwave irradiation-assisted transesterification of soybean oil to biodiesel catalyzed by nanopowder calcium oxide

This study examined the effect of a heterogeneous base catalyst on the transesterification of soybean oil assisted by microwave irradiation. The results showed that nanopowder calcium oxide (nano CaO) was very efficient in converting soybean oil to biodiesel, and microwave irradiation is more efficient than the conventional bath for biodiesel production. However, the water content of methanol can not improve the conversion rate catalyzed by nano CaO.The suitable reaction conditions that can reach a 96.6% of conversion rate were methanol/oil molar ratio, 7:1; amount of catalyst used, 3.0 wt.%; reaction temperature, 338 K; and reaction time, 60 min. The biodiesel produced is within the limits prescribed by the standard of EN-14214.     

Influence of the glycerin content in the preparation of calcium diglyceroxide from eggshell applied in the residual oil transesterification

Currently, biodiesel is pointed out worldwide as the main alternative in the complementation and substitution of petrochemical diesel. However, the current industrial route of synthesis of this biofuel depends on the cost of raw materials (which are also destined for food purposes) and the expense of the production process. Aiming to remedy this obstacle, the use of solid, sustainable, low-cost, efficient, and reusable catalysts in residual raw materials, such as waste cooking oils, has been highlighted as a promising alternative. This work focused on studying the influence of the glycerin content used in the preparation by wet impregnation of catalyst calcium diglyceroxide in the efficiency of transesterification of waste cooking oil. The catalyst was synthesized from CaO from chicken eggshell, raw glycerin co-product from biodiesel, and methanol. The transesterification reactions were performed using 120 g of frying residual oil, methanol: oil molar rate of 6:1, constant shaking, and reaction temperature of 63 ± 1°C for 180 min. The catalyst material synthesized with residual glycerin was active for four reactions (without reactivation of its sites) with high percentages of efficiency of 96.13, 96.85, 95.93, and 91.65, respectively. It was noted that the glycerol purity correlated with changes in the structural morphology of the final compound, as well as changes in the leaching rate, acidity index, water content, and ester content of the blends. It was found that adding 15% water to the lipid material correlated with an increase in ester content (99%) in the synthesized biodiesel.     

Waste Frying Oils as Substrate for Enzymatic Lipolysis: Optimization of Reaction Conditions in O/W Emulsion

Waste frying oils (WFO) can be both environmental pollutants and a source of valuable products. In this work we explore the conversion of WFO into surface‐active substances, such as FFA and partial glycerides, through enzymatic hydrolysis in O/W emulsion. Two different WFO and three lipases of different origin were tested. In addition, we optimized the conditions for the production of O/W emulsions to be used as reaction medium as well as several reaction parameters, such as the type of enzyme and its concentration, the pH, and the presence of Ca²⁺ ions. Gum arabic‐stabilized emulsions with an oil fraction of 0.15 proved to be the most adequate owing to their high interfacial area and short‐term stability. The physicochemical characterization of both WFO revealed the presence of an increased amount of surface‐active matter relative to food‐grade vegetable oils. These substances, mainly FFA, can interfere with lipase action and reduce the reaction rate. However, the extent of hydrolysis was only slightly affected by them, and remained fairly similar to that achieved with a control mixture of food‐grade vegetable oils. The product distribution depended on the enzyme used. Pseudomonas fluorescens lipase was found to be particularly suitable for the production of partial glycerides (mono‐ and diacylglycerols), which are in great demand by the food industry. In any case our results demonstrate that WFO are a good substrate for enzymatic hydrolysis, comparable to food‐grade vegetable oils, providing an alternative route for the valorization of this waste.     

Phytostanol Supplementation Through Frying Dough in Enriched Canola Oil

The objectives of this study were to determine a suitable level of phytostanols for addition to canola oil and to investigate the performance of the supplemented oil during frying. The frying oil was supplemented with 5, 10, 15, 20 % w/w phytostanols and two suitable levels (5 and 10 %) were selected. Dough frying was performed for 5 consecutive days at 180 °C for 5 h/day. The ranges of analytical measurements in the treatment groups were; free acidity (0.12–10.07 %), conjugated dienes (0.47–1.37 %), total polar material with probe (9.00–51.25 %), viscosity (46.27–195.51 cP), turbidity (0.82–1.80 NTU), and smoke point (202.75–274.25 °C). The results indicated that 5 % phytostanol enriched oil was superior in terms of oil stability and sensory quality of the fried dough among all the enriched oils. Samples with 10 % added phytostanols were high in free acidity, conjugated dienes and smoke points. Sterol composition analysis showed that the fried dough absorbed total sterols of 49.9 and 95 g/kg in 5 and 10 % supplemented oils, respectively. Hence, some health benefits could be achieved through consuming products which have been fried in phytostanol supplemented canola oil.     

Microwave assisted in continuous biodiesel production from waste frying palm oil and its performance in a 100 kW diesel generator

A household microwave (800W) was modified as a biodiesel reactor for continuous transethylation of waste frying palm oil. The high free fatty acid oil was simultaneously neutralized and transesterified with sodium hydroxide. With the ethanol to oil molar ratio of 12:1, 3.0% NaOH (in ethanol) and 30s residence time, the continuous conversion of waste frying palm oil to ethyl ester was over 97%. The waste palm oil biodiesel was then tested in a 100 kW diesel generator as a neat fuel (B100) and 50% blend with diesel No. 2 fuel (B50). The engine performance and emission are recorded. At the engine loads varied from 0 kW to 75 kW (at 25 kW intervals) of the maximum electrical rating, the performance of the neat and B50 are slightly lower than diesel No. 2 fuel. Emissions of NO_x, CO and HC from B100 and B50 are lower than those of diesel No. 2 fuel, except that at the 75 kW engine load, where the B100 emits higher levels of NO_x than the diesel No. 2 fuel.     

Biodiesel production from Jerusalem artichoke (Helianthus Tuberosus L.) tuber by heterotrophic microalgae Chlorella protothecoides

BACKGROUND: As a potential source of biomass, Jerusalem artichoke has been studied for bioethanol production; however, thus far it has not been investigated for the production of other liquid biofuels, such as biodiesel. This work aims to develop a novel approach for biodiesel production from Jerusalem artichoke tuber using heterotrophic microalgae. RESULTS: In this study, Chlorella protothecoides utilized hydrolysate of Jerusalem artichoke tuber as carbon source and accumulated lipid in vivo, with lipid content as high as 44% by dry mass, and a carbon source to lipid conversion ratio of about 25% in a 4‐day scale cultivation. The lipids were extracted and then converted into biodiesel by transesterification. Cetane acid methyl ester, linoleic acid methyl ester and oleic acid methyl ester were the dominating components of the biodiesel produced. Unsaturated fatty acids methyl ester constituted over 82% of the total biodiesel content. CONCLUSION: This work suggests the feasibility of an alternative method of producing biodiesel from Jerusalem artichoke tuber using microalgae cultivation, and a cost reduction of carbon source feed in algal oil production can be expected. Copyright © 2009 Society of Chemical Industry