In situ Real-Time Multivariate Analysis of Methanolysis Monitoring of Sunflower Oil Using FTIR

The combination of world population and the third industrial revolution led to high demand for fuels. On the other hand, the decrease of global fossil 8fuels deposits and the environmental air pollution caused by these fuels has compounded the challenges the world faces due to its need for energy. Therefore, new forms of environmentally friendly and renewable fuels such as biodiesel are needed. The primary analytical techniques for methanolysis yield monitoring have been chromatography and spectroscopy, these methods have been proven reliable but are more demanding, costly and do not provide real-time monitoring. In this work, the in situ monitoring of biodiesel from sunflower oil using FTIR (Fourier Transform Infrared) has been studied; the study was performed using EasyMax Mettler Toledo reactor equipped with a DiComp (Diamond) probe. The quantitative monitoring of methanolysis was performed by building a quantitative model with multivariate calibration using iC Quant module from iC IR 7.0 software. 15 samples of known concentrations were used for the modelling which were taken in duplicate for model calibration and cross-validation, data were pre-processed using mean centering and variance scale, spectrum math square root and solvent subtraction. These pre-processing methods improved the performance indexes from 7.98 to 0.0096, 11.2 to 3.41, 6.32 to 2.72, 0.9416 to 0.9999, RMSEC, RMSECV, RMSEP and R2Cum, respectively. The R2 value of 1 (training), 0.9918 (test), 0.9946 (cross-validation) indicated the fitness of the model built. The model was tested against univariate model; small discrepancies were observed at low concentration due to unmodelled intermediates but were quite close at concentrations above 18%. The software eliminated the complexity of the Partial Least Square (PLS) chemometrics. It was concluded that the model obtained could be used to monitor methanol of sunflower oil at industrial and lab scale.

Optimization of Biodiesel Production from Sunflower Oil Using Central Composite Design

The current study investigated the effect of catalyst ratio and methanol to oil ratio on biodiesel production by using central composite design. Biodiesel was produced by transesterification using sodium hydroxide as a homogeneous catalyst, a laboratory scale reactor consisting of flat bottom flask mounts with a reflux condenser, and a heating plate was used to produce biodiesel. Key parameters, including time, temperature, and mixing rate was kept constant at 60 minutes, 60 oC and 600 RPM, respectively. From the results obtained, it was observed that the biodiesel yield depends on catalyst ratio and methanol to oil ratio. The highest yield of 50.65% was obtained at catalyst ratio of 0.5 wt.% and methanol to oil mole ratio 10.5. The analysis of variances of biodiesel yield showed the R Squared value of 0.8387. A quadratic mathematical model was developed to predict the biodiesel yield in the specified parameters ranges.

Quality Evaluation of Grape Seed Oils of the Ionian Islands Based on GC-MS and Other Spectroscopic Techniques

Grape seeds are waste products of wineries and often referred to as an important agricultural and industrial waste product with the potential to be used in pharmaceutical, food, and cosmetic applications. In this study, grape seed oil from traditional Ionian varieties was examined for the determination of the quality and the characteristics of each variety. Initially, the fatty acid methyl ester (FAME) profiles were analyzed using Gas Chromatography-Mass Spectrometry, after transesterification. Furthermore, other quality parameters of the grape seed oils were determined by Spectroscopy techniques, UV-Vis and Raman included. Moreover, the antioxidant capacity of the oil was measured by 2,2'-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) and 2,2-Diphenyl-1-picrylhydrazyl (DPPH) assays and their antioxidant capacity expressed in Trolox equivalents. K and ΔΚ indices were measured in 232, 268, 270 nm, as an oil quality index. The results indicate that the air-dried grape seed total oil content ranged from 5.26 to 8.77% w/w, which is in accordance with the other grape seed varieties tested in similar studies. The composition of grape seed oil is predominated with linoleic and oleic fatty acids, with the linoleic fatty acid ranging from 53.68 to 69.95% and both the linoleic and oleic fatty acids totaling 78-82% of FAMEs, which is analogous to the fatty acid composition of safflower oil. The antioxidant assays ABTS and DPPH scored high, exhibiting that the oils have potential in the cosmetic and culinary businesses. Above that, our results demonstrate that Ionian grape seed oils have prospects that can go further than cosmetic or culinary use, into the pharmaceuticals industry. Finally, the reclamation of grape seeds from wineries waste stream is in accordance with the bio-economy strategic framework and contributes to environmental protection.

Biodiesel Production from Palm Oil Using an Oscillatory Baffled Reactor

Biofuel production especially that of biodiesel has gained tremendous attention during the last decade due to environmental concerns and shortage in petroleum oil reservoir. This research aims to investigate the influences of operating parameters, such as the alcohol-to-oil molar ratio (4:1, 6:1, and 9:1) and the amount of catalyst (1, 1.5, and 2 wt.%) on the trans esterification of refined palm oil (RPO) in a medium-scale oscillatory baffle reactor.  It has been shown that an increase in the methanol-to-oil ratio resulted in an increase in fatty acid methyl esters (FAMEs) content. The amount of catalyst has an insignificant effect on the FAMEs content. Engine testing was performed on B0 (100 v/v% diesel) and blended fuel or B50 (50 v/v% diesel). Combustion of B50 was found to give lower torque compared to pure diesel. Exhaust gas from B50 was found to contain lower concentration of CO and CO2.

Fatty Acid and Amino Acid Composition in Mene maculata in The Sea of Maluku

Fish is a kind of food that contains many nutritions, one of those is the long chain of unsaturated fatty acids as omega-3 and omega-6 fatty acids and essential amino acid in enough amount for the necessity of our body. Like pelagic fish that found in the sea of Maluku. This research was done to identify fatty acids and amino acids composition in Moonfish (M. maculata) using transesterification reaction steps and Gas Chromatograph-Mass Spectrophotometer (GC-MS) and High-Performance Liquid Chromatography (HPLC). The result showed that fatty acids composition in Moonfish (M. maculata) contained tridecanoic acid (2.84%); palmitoleic acid (2.65%); palmitic acid (35.24%); oleic acid (6.2%); stearic acid (14.20%); and 5,8,11,14-eicosatetraenoic acid (1.29%) and 12 amino acids composition that consist of 7 essential amino acids, were leucine, isoleucine, valine, phenylalanine, methionine, lysine, and histidine, and also 5 non-essential amino acid, were tyrosine, glycine, alanine, glutamic acid, and arginine.Thus, these fishes can be used by the people to complete the necessity of essential fatty acid and amino acid.

Optimization of Biodiesel Production from Sunflower Oil Using Central Composite Design

The current study investigated the effect of catalyst ratio and methanol to oil ratio on biodiesel production by using central composite design. Biodiesel was produced by transesterification using sodium hydroxide as a homogeneous catalyst, a laboratory scale reactor consisting of flat bottom flask mounts with a reflux condenser and a heating plate was used to produce biodiesel. Key parameters, including, time, temperature and mixing rate were kept constant at 60 minutes, 60 oC and 600 RPM, respectively. From the results obtained, it was observed that the biodiesel yield depends on catalyst ratio and methanol to oil ratio. The highest yield of 50.65% was obtained at catalyst ratio of 0.5 wt.% and methanol to oil mole ratio 10.5. The analysis of variances of biodiesel yield showed the R Squared value of 0.8387. A quadratic mathematical model was developed to predict the biodiesel yield in the specified parameters ranges.

Intensification of Ethyl Esters Synthesis Using a Packed-Bed Tubular Reactor at Supercritical Conditions

In the present study, the non-catalytic transesterification of soybean oil in continuous mode using supercritical ethanol were investigated. Experiments were performed in a packed-bed tubular reactor (PBTR) and variable studied were reaction temperature (523 K to 598 K), pressure (10 MPa to 20 MPa), oil to ethanol molar ratio (1:10 to 1:40) and water concentration (0 wt% to 10 wt% in ethanol). Results showed that ethyl esters yields obtained in the PBTR were higher (> 20 wt%) than those verified in a tubular reactor (TR), due to improved mass transfer conditions attained in the PBTR. Results demonstrated that temperature, pressure, oil to ethanol molar ratio and water concentration had a positive effect on fatty acid ethyl esters (FAEE) production in the experimental range investigated, with appreciable reaction yields (90 wt%) achieved at 598 K, 20 MPa, oil to ethanol molar ratio of 1:40 and 10 wt% of water concentration.

Transesterification of Waste Cooking Oil for Biodiesel Production Using Modified Clinoptilolite Zeolite as a Heterogeneous Catalyst

Reduction of fossil fuels sources, increasing of pollution gases emission, and global warming effects increase the demand of renewable fuels. One of the main candidates of alternative fuels is biodiesel. Biodiesel limits greenhouse gas effects due to the closed CO2 cycle. Biodiesel has more biodegradability, lower combustion emissions such as CO, SOx, HC, PM and lower toxicity than petro diesel. However, biodiesel has high production cost due to high price of plant oils as raw material. So, the utilization of waste cooking oils (WCOs) as feedstock, due to their low price and disposal problems reduce biodiesel production cost. In this study, production of biodiesel by transesterification of methanol and WCO using modified sodic potassic (SP) clinoptilolite zeolite and sodic potassic calcic (SPC) clinoptilolite zeolite as heterogeneous catalysts have been investigated. These natural clinoptilolite zeolites were modified by KOH solution to increase the site activity. The optimum biodiesel yields for SP clinoptilolite and SPC clinoptilolite were 95.8% and 94.8%, respectively. Produced biodiesel were analyzed and compared with petro diesel and ASTM limits. The properties of produced biodiesel confirm well with ASTM limits. The density, kinematic viscosity, cetane index, flash point, cloud point, and pour point of produced biodiesel were all higher than petro diesel but its acid value was lower than petro diesel. Finally, the reusability and regeneration of catalysts were investigated. The results indicated that the spent zeolites cannot be reused directly for the transesterification, but they can be regenerated easily and can obtain high activity.

Reaction Kinetics of Biodiesel Production from Refined Cottonseed Oil Using Calcium Oxide

Power law approximation was used in this study to evaluate the reaction orders of calcium oxide, CaO catalyzed transesterification of refined cottonseed oil and methanol. The kinetics study was carried out at temperatures of 45, 55 and 65 oC. The kinetic parameters such as reaction order 2.02 and rate constant 2.8 hr-1g-1cat, obtained at the temperature of 65 oC best fitted the kinetic model. The activation energy, Ea obtained was 127.744 KJ/mol. The results indicate that the transesterification reaction of the refined cottonseed oil using calcium oxide catalyst is approximately second order reaction.

Vapor Phase Transesterification of Dimethyl Malonate with Phenol over Cordierite Honeycomb Coated with Zirconia and Its Modified Forms

The transesterification of dimethyl malonate (DMM) with phenol has been studied in vapour phase over cordierite honeycomb coated with solid acid catalysts such as ZrO2, Mo(VI)/ZrO2 and SO42-/ZrO2. The catalytic materials were prepared honeycomb coated, powder forms, and characterized for their total surface acidity by NH3-TPD and crystalinity by powder XRD methods. Phenyl methyl malonate (PMM) and diphenyl malonate (DPM) were obtained as the reaction products. A good conversion of DMM (up to 82%) of MPM with 95% selectivity was observed when the reactions were carried out at a catalyst bed temperature of 200 °C and flow-rate of 10 mL/h in presence of Mo(VI)/ZrO2 as catalyst. However, over SO4^2-/ZrO2 catalyst, the yield of DPM was found to be higher. The results have been interpreted based on the variation of acidic properties and powder XRD phases of zirconia on incorporation of Mo(VI) or SO42– ions. Transesterification reactions were also carried out over powder forms of the catalytic materials and the yield of the desired phenyl ester products were compared with that of the HC coated catalytic materials. The solid acids were found to be reusable when used for at least 5 reaction cycles.

Biodiesel Production from Broiler Chicken Waste

Broiler slaughter waste has become a major source of pollution throughout the world. Utilization of broiler slaughter waste by dry rendering process produced Rendered Chicken Oil (RCO), a cheap raw material for biodiesel production and Carcass Meal a feed ingredient for pets and fishes. Conversion of RCO into biodiesel may open new vistas for generating wealth from waste besides controlling the major havoc of environmental pollution. A two-step process to convert RCO to good quality Biodiesel was invented. Acid catalysed esterification of FFA followed by base catalysed transesterification of triglycerides was carried out after meticulously standardizing the methanol molar ratio, catalyst concentration, reaction temperature, and reaction time to obtain the maximum biodiesel yield of 97.62% and lowest glycerol yield of 6.96%. RCO biodiesel blend was tested in a CRDI diesel engine. The results revealed that the blending of commercial diesel with 20% RCO biodiesel (B20) lead to less engine wear, a quieter engine and better fuel economy. The better lubricating qualities of RCO B20 prevented over heating of engine, which prolongs the engine life. RCO B20 can reduce the import of crude oil and substantially reduce the engine emissions as proved by significantly lower smoke levels, thus mitigating climatic changes.

Microwave Assisted Solvent-Free Catalytic Transesterification of Glycerol to Glycerol Carbonate

As a by-product of the biodiesel industries, glycerol has been vastly generated which surpasses the market demand. It is imperative to develop an efficient glycerol valorization processes in minimizing the net energy requirement and intensifying the biodiesel production. In this study, base-catalyzed transesterification of glycerol with dimethyl carbonate using microwave irradiation as heating method to produce glycerol carbonate was conducted by varying grades of glycerol, i.e. 70%, 86% and 99% purity, that is obtained from biodiesel plant. Metal oxide catalysts were used with varying operating parameters including reaction time, DMC/glycerol molar ratio, catalyst weight %, temperature and stirring speed. From the study on the effect of different operating parameters it was found that the type of catalyst used has the most significant effect on the transesterification reaction. Amidst the metal oxide catalysts examined, CaO gave the best performance. This study indicates the feasibility of producing glycerol carbonate using different grade of glycerol in both conventional thermal activation and microwave irradiation with CaO as catalyst. Microwave assisted transesterification (MAT) of glycerol into glycerol carbonate has demonstrated itself as an energy efficient route by achieving 94.2% yield of GC at 65°C, 5 minutes reaction time, 1 wt% CaO and DMC/glycerol molar ratio of 2. The advantages of MAT transesterification route has made the direct utilization of bioglycerol from biodiesel production without the need of purification. This has marked a more economical and less-energy intensive glycerol carbonate synthesis route.

Influence of Synthetic Antioxidant in the Iodine Value and Acid Number of Jatropha Curcas Biodiesel

Biodiesel is one of the alternative fuels that promising for substituting petro diesel as energy source which is advantage on sustainability and ecofriendly. Due to the raw material that tend to decompose during storage, biodiesel also have the same characteristic that tend to decompose and formed higher acid value which is the result of oxidation to double bond on a chain of ester. Decomposition of biodiesel due to oxidation reaction could prevent by introduce a small amount of antioxidant. The origin of raw materials and the process for producing biodiesel will determine the effectiveness of antioxidant. The quality degradation on biodiesel could evaluate by measuring iodine value and acid number of biodiesel. Biodiesel made from high fatty acid Jatropha curcas oil by using esterification and transesterification process will stand on the quality by introduce 90 ppm pyrogallol powder on the biodiesel, which could increase Induction period time from 2 hours to more than 6 hours in rancimat test evaluation.

Properties of Biodiesel Produced by Enzymatic Transesterification of Lipids Extracted from Microalgae in Supercritical Carbon Dioxide Medium

Biodiesel, as an alternative renewable fuel, has been receiving increasing attention due to the limited supply of fossil fuels and the increasing need for energy. Microalgae are promising source for lipids, which can be converted to biodiesel. The biodiesel production from microalgae lipids using lipase catalyzed reaction in supercritical CO2 medium has several advantages over conventional production processes. However, identifying the optimum microalgae lipid extraction and transesterification conditions is still a challenge. In this study, the quality of biodiesel produced from lipids extracted from Scenedesmus sp. and their enzymatic transesterification using supercritical carbon dioxide have been investigated. At the optimum conditions, the highest biodiesel production yield was found to be 82%. The fuel properties of the produced biodiesel, without any separation step, at optimum reaction condition, were determined and compared to ASTM standards. The properties were found to comply with the limits, and showed a low glycerol content, without any separation step.

Thermal Cracking Approach Investigation to Improve Biodiesel Properties

Biodiesel as an alternative diesel fuel is steadily gaining more attention and significance. However, there are some drawbacks while using biodiesel regarding its properties that requires it to be blended with petrol based diesel and/or additives to improve the fuel characteristics. This study analyses thermal cracking as an alternative technology to improve biodiesel characteristics in which, FAME based biodiesel produced by transesterification of castor oil is fed into a continuous thermal cracking reactor at temperatures range of 450-500°C and flowrate range of 20-40 g/hr. Experiments designed by response surface methodology and subsequent statistical studies show that temperature and feed flowrate significantly affect the products yield. Response surfaces were used to study the impact of temperature and flowrate on the product properties. After each experiment, the produced crude bio-oil was distilled and diesel cut was separated. As shorter chain molecules are produced through thermal cracking, the distillation curve of the diesel cut fitted more with petrol based diesel curve in comparison to the biodiesel. Moreover, the produced diesel cut properties adequately pose within property ranges defined by the related standard of petrol based diesel. Cold flow properties, high heating value as the main drawbacks of the biodiesel are improved by this technology. Thermal cracking decreases kinematic viscosity, Flash point and cetane number. 

Kinetic Modeling of Transesterification of Triacetin Using Synthesized Ion Exchange Resin (SIERs)

Strong anion exchange resins with QN+OH-, have the potential to be developed and employed as heterogeneous catalyst for transesterification, as they are chemically stable to leaching of the functional group. Nine different SIERs (SIER1-9) with QN+OH-were prepared by suspension polymerization of vinylbenzyl chloridedivinylbenzene (VBC-DVB) copolymers in the presence of n-heptane (pore-forming agent). The amine group was successfully grafted into the polymeric resin beads through functionalization with trimethylamine. These SIERs are then used as a catalyst for the transesterification of triacetin with methanol. A set of differential equations that represents the Langmuir-Hinshelwood-Hougen- Watson (LHHW) and Eley-Rideal (ER) models for the transesterification reaction were developed. These kinetic models of LHHW and ER were fitted to the experimental data. Overall, the synthesized ion exchange resin-catalyzed reaction were welldescribed by the Eley-Rideal model compared to LHHW models, with sum of square error (SSE) of 0.742 and 0.996, respectively.

Conversion of Jatropha curcas Oil to Ester Biolubricant Using Solid Catalyst Derived from Saltwater Clam Shell Waste (SCSW)

The discarded clam shell waste, fossil and edible oil as biolubricant feedstocks create environmental impacts and food chain dilemma, thus this work aims to circumvent these issues by using activated saltwater clam shell waste (SCSW) as solid catalyst for conversion of Jatropha curcas oil as non-edible sources to ester biolubricant. The characterization of solid catalyst was done by Differential Thermal Analysis-Thermo Gravimetric Analysis (DTATGA), X-Ray Fluorescence (XRF), X-Ray Diffraction (XRD), Brunauer-Emmett-Teller (BET), Field Emission Scanning Electron Microscopy (FESEM) and Fourier Transformed Infrared Spectroscopy (FTIR) analysis. The calcined catalyst was used in the transesterification of Jatropha oil to methyl ester as the first step, and the second stage was involved the reaction of Jatropha methyl ester (JME) with trimethylolpropane (TMP) based on the various process parameters. The formated biolubricant was analyzed using the capillary column (DB-5HT) equipped Gas Chromatography (GC). The conversion results of Jatropha oil to ester biolubricant can be found nearly 96.66%, and the maximum distribution composition mainly contains 72.3% of triester (TE).

Tribological Investigation and the Effect of Karanja Biodiesel on Engine Wear in Compression Ignition Engine

Various biomass based resources, which can be used as an extender, or a complete substitute of diesel fuel may have very significant role in the development of agriculture, industrial and transport sectors in the energy crisis. Use of Karanja oil methyl ester biodiesel in a CI DI engine was found highly compatible with engine performance along with lower exhaust emission as compared to diesel fuel but with slightly higher NOx emission and low wear characteristics. The combustion related properties of vegetable oils are somewhat similar to diesel oil. Neat vegetable oils or their blends with diesel, however, pose various long-term problems in compression ignition engines. These undesirable features of vegetable oils are because of their inherent properties like high viscosity, low volatility, and polyunsaturated character. Pongamia methyl ester (PME) was prepared by transesterification process using methanol for long term engine operations. The physical and combustion-related properties of the fuels thus developed were found to be closer to that of the diesel. A neat biodiesel (PME) was selected as a fuel for the tribological study of biofuels. Two similar new engines were completely disassembled and subjected to dimensioning of various vital moving parts and then subjected to long-term endurance tests on neat biodiesel and diesel respectively. After completion of the test, both the engines were again disassembled for physical inspection and wear measurement of various vital parts. The lubricating oil samples drawn from both engines were subjected to atomic absorption spectroscopy (AAS) for measurement of various wear metal traces present. The additional lubricating property of biodiesel fuel due to higher viscosity as compared to diesel fuel resulted in lower wear of moving parts and thus improved the engine durability with a bio-diesel fuel. Results reported from AAS tests confirmed substantially lower wear and thus improved life for biodiesel operated engines.

Characterization of Fish Bone Catalyst for Biodiesel Production

In this study, fish bone waste was used as a new catalyst for biodiesel production. Instead of discarding the fish bone waste, it will be utilized as a source for catalyst that can provide significant benefit to the environment. Also, it can be substitute as a calcium oxide source instead of using eggshell, crab shell and snail shell. The XRD and SEM analysis proved that calcined fish bone contains calcium oxide, calcium phosphate and hydroxyapatite. The catalyst was characterized using Scanning Electron Microscope (SEM) and X-ray Diffraction (XRD).

Transesterification of Jojoba Oil-Wax Using Microwave Technique

Jojoba oil-wax is extracted from the seeds of the jojoba (Simmondsia chinensis Link Schneider), a perennial shrub that grows in semi desert areas in Egypt and in some parts of the world. The main uses of jojoba oil-wax are in the cosmetics and pharmaceutical industry, but new uses could arise related to the search of new energetic crops. This paper summarizes a process to convert the jojoba oil-wax to biodiesel by transesterification with ethanol and a series of aliphatic alcohols using a more economic and energy saving method in a domestic microwave. The effect of time and power of the microwave on the extent of the transesterification using ethanol and other aliphatic alcohols has been studied. The separation of the alkyl esters from the fatty alcohols rich fraction has been done in a single crystallization step at low temperature (−18°C) from low boiling point petroleum ether. Gas chromatography has been used to follow up the transesterification process. All products have been characterized by spectral analysis.