Application of waste eggshell as low-cost solid catalyst for biodiesel production

Waste eggshell was investigated in triglyceride transesterification with a view to determine its viability as a solid catalyst for use in biodiesel synthesis. Effect of calcination temperature on structure and activity of eggshell catalysts was investigated. Reusability of eggshell catalysts was also examined. It was found that high active, reusable solid catalyst was obtained by just calcining eggshell. Utilization of eggshell as a catalyst for biodiesel production not only provides a cost-effective and environmental friendly way of recycling this solid eggshell waste, significantly reducing its environmental effects, but also reduces the price of biodiesel to make biodiesel competitive with petroleum diesel.     

Heterogeneous solid base nanocatalyst: preparation, characterization and application in biodiesel production

A solid base nanocatalyst was prepared by ZrO₂ loaded with C₄H₄O₆HK and investigated for transesterification of soybean oil with methanol to biodiesel. The obtained nanocatalyst was characterized by means of XRD, FTIR, TEM, TGA, N₂ adsorption-desorption measurements and the Hammett indicator method. TEM photograph showed that the nanocatalyst had granular and porous structures with particle sizes of 10-40 nm. The nanocatalyst had longer lifetime and maintained sustained activity after being used for five cycles. The separate effects of the molar ratio of methanol to oil, reaction temperature, nanocatalyst amount and reaction time were investigated. The experimental results showed that a 16:1 M ratio of methanol to oil, 6.0% catalyst, 60 °C reaction temperature and 2.0 h reaction time gave the best results and the biodiesel yield of 98.03% was achieved. Production of biodiesel has positive impact on the utilization of agricultural and forestry products.     

Production of algae-based biodiesel using the continuous catalytic Mcgyan® process

This study demonstrates the production of algal biodiesel from Dunaliella tertiolecta, Nannochloropsis oculata, wild freshwater microalgae, and macroalgae lipids using a highly efficient continuous catalytic process. The heterogeneous catalytic process uses supercritical methanol and porous titania microspheres in a fixed bed reactor to catalyze the simultaneous transesterification and esterification of triacylglycerides and free fatty acids, respectively, to fatty acid methyl esters (biodiesel). Triacylglycerides and free fatty acids were converted to alkyl esters with up to 85% efficiency as measured by 300 MHz ¹H NMR spectroscopy. The lipid composition of the different algae was studied gravimetrically and by gas chromatography. The analysis showed that even though total lipids comprised upwards of 19% of algal dry weight the saponifiable lipids, and resulting biodiesel, comprised only 1% of dry weight. Thus highlighting the need to determine the triacylglyceride and free fatty acid content when considering microalgae for biodiesel production.     

Silica-bonded N-propyl sulfamic acid used as a heterogeneous catalyst for transesterification of soybean oil with methanol

The transesterification of soybean oil with methanol was carried out, to produce biodiesel, over silica-bonded N-propyl sulfamic acid in a heterogeneous manner. Results showed that a maximum conversion of 90.5% was achieved using a 1:20 M ratio of soybean oil to methanol and a catalyst amount of 7.5 wt.% at 423 K for 60 h. It was found that the free fatty acid (FFA) and water present in the feedstock had no significant influence on the catalytic activity to the transesterification reaction. Besides, the catalyst also showed activities towards the esterification reaction of FFAs, in terms of the FFA conversion of 95.6% at 423 K for 30 h. Furthermore, the catalyst could be recovered with a better reusability.     

Study of biodiesel production from animal fats with high free fatty acid content

The aim of this work was to obtain biodiesel from animal fats, an inedible feedstock. Three different types of fats were used to produce biodiesel; their main characteristic was high free fatty acid content. Animal fats were transesterified with acid catalyst and basic catalyst with and without pre-esterification. Biodiesel of 89.0 wt.% ester content was obtained by acid-transesterification (9 wt.% H₂SO₄, 6:1 methanol:fats molar ratio, 60 °C, 48 h). Pre-esterification conditions were studied for different fats and acid catalysts: 0.5 wt.% H₂SO₄ or 1.0 wt.% p-TsOH, 6:1 methanol:fats molar ratio, 65 °C and 4 h made it possible to obtain fats with acid value less than 0.5% FFA. Pre-treatment was effective for fats with different FFA content. Alkali transesterification of esterified fats resulted in a product with 97.3 wt.% ester content. Biodiesel quality was evaluated and most of properties were well within EN 14214.     

Production of biodiesel from acid waste lard

The objective of the present work was: (i) to enable biodiesel production from acid waste lard; (ii) to study the esterification reaction as possible pre-treatment at different temperatures, catalyst amount and reaction times; (iii) to evaluate biodiesel quality according to EN 14214 after basic transesterification of the pre-treated fat; and (iv) to predict the impact of using such waste as raw material in mixture with soybean oil. Temperature and catalyst amount were the most important reaction conditions which mostly affected biodiesel quality, namely viscosity and purity. The selected pre-treatment conditions were 65 °C, 2.0 wt% H₂SO₄ and 5 h, which allowed obtaining a product with a viscosity of 4.81 mm² s⁻¹ and a purity of 99.6 wt%. The proposed pre-treatment was effective to enable acid wastes as single raw materials for biodiesel production with acceptable quality; however, low yields were obtained (65 wt%). Alkali transesterification of a mixture of waste lard and soybean oil resulted in a product with a purity of 99.8 wt% and a yield of 77.8 wt%, showing that blending might be an interesting alternative to recycle such wastes. Also, because in addition to using conventional and relatively economical processes, some biodiesel properties depending on the raw material composition (such as the iodine value) might even be improved.     

Methods of downstream processing for the production of biodiesel from microalgae

Despite receiving increasing attention during the last few decades, the production of microalgal biofuels is not yet sufficiently cost-effective to compete with that of petroleum-based conventional fuels. Among the steps required for the production of microalgal biofuels, the harvest of the microalgal biomass and the extraction of lipids from microalgae are two of the most expensive. In this review article, we surveyed a substantial amount of previous work in microalgal harvesting and lipid extraction to highlight recent progress in these areas. We also discuss new developments in the biodiesel conversion technology due to the importance of the connectivity of this step with the lipid extraction process. Furthermore, we propose possible future directions for technological or process improvements that will directly affect the final production costs of microalgal biomass-based biofuels.     

Ethanesulfonic acid-based esterification of industrial acidic crude palm oil for biodiesel production

An industrial grade acidic crude palm oil (ACPO) pre-treatment process was carried out using ethanesulfonic acid (ESA) as a catalyst in the esterification reaction. ESA was used in different dosages to reduce free fatty acid (FFA) to a minimum level for the second stage of biodiesel production via alkaline transesterification reaction. Different process operating conditions were optimized such as ESA dosage (0.25-3.5% wt/wt), methanol to ACPO molar ratio (1:1-20:1), reaction temperature (40-70 °C), and reaction time (3-150 min). This study revealed the potential use of abundant quantities of ACPO from oil palm mills for biodiesel production. The lab scale results showed the effectiveness of the pre-treatment process using ESA catalyst. Three consecutive catalyst recycling runs were achieved without significant degradation in its performance. Second and third reuse runs needed more reaction time to achieve the target level of FFA content. Esterification and transesterification using ESA and KOH respectively is proposed for biodiesel industrial scale production. The produced biodiesel meets the international standards specifications for biodiesel fuel (EN 14214 and ASTM D6751).     

Use of experimental design to investigate biodiesel production by multiple-stage Ultra-Shear reactor

This work presents biodiesel production from soybean oil and bioethanol by multiple-stage Ultra-Shear reactor (USR). The experiments were carried out in the following conditions: reaction time from 6 to 12 min; catalyst concentration from 0.5% to 1.5% by weight of soybean oil; ethanol: soybean oil molar ratio from 6:1 to 10:1. The experimental design was used to investigate the influence of process variables on the conversion in biodiesel. The best ethyl ester conversion obtained was 99.26 wt.%, with ethanol:soybean oil molar ratio of 6:1, catalyst concentration of 1.35% and with 12 min of reaction time.     

Synthesis of methyl esters from palm (Elaeis guineensis) oil using cobalt doped MgO as solid oxide catalyst

The potential of Mg(x)Co(2-)(x)O(2) as heterogeneous reusable catalyst in transesterification of palm oil to methyl ester was investigated. The catalyst was prepared via co-precipitation of the metal hydroxides at different Mg-Co ratios. Mg(1.7)Co(0.3)O(2) catalyst was more active than Mg(0.3)Co(1.7)O(2) in the transesterification of palm oil with methanol. The catalysts calcined at temperature 300 °C for 4 h resulted in highly active oxides and the highest transesterification of 90% was achieved at methanol/oil molar ratio of 9:1, catalyst loading of 5.00 wt.%, reaction temperature of 150 °C and reaction time of 2 h. The catalyst could easily be removed from reaction mixture, but showed 50% decrease in activity when reused due to leaching of active sites.     

Homogeneous,heterogeneous and enzymatic catalysis for transesterification of high free fatty acid oil (waste cooking oil) to biodiesel: A review

In the last few years, biodiesel has emerged as one of the most potential renewable energy to replace current petrol-derived diesel. It is a renewable, biodegradable and non-toxic fuel which can be easily produced through transesterification reaction. However, current commercial usage of refined vegetable oils for biodiesel production is impractical and uneconomical due to high feedstock cost and priority as food resources. Low-grade oil, typically waste cooking oil can be a better alternative; however, the high free fatty acids (FFA) content in waste cooking oil has become the main drawback for this potential feedstock. Therefore, this review paper is aimed to give an overview on the current status of biodiesel production and the potential of waste cooking oil as an alternative feedstock. Advantages and limitations of using homogeneous, heterogeneous and enzymatic transesterification on oil with high FFA (mostly waste cooking oil) are discussed in detail. It was found that using heterogeneous acid catalyst and enzyme are the best option to produce biodiesel from oil with high FFA as compared to the current commercial homogeneous base-catalyzed process. However, these heterogeneous acid and enzyme catalyze system still suffers from serious mass transfer limitation problems and therefore are not favorable for industrial application. Nevertheless, towards the end of this review paper, a few latest technological developments that have the potential to overcome the mass transfer limitation problem such as oscillatory flow reactor (OFR), ultrasonication, microwave reactor and co-solvent are reviewed. With proper research focus and development, waste cooking oil can indeed become the next ideal feedstock for biodiesel.     

Study on acyl migration in immobilized lipozyme TL-catalyzed transesterification of soybean oil for biodiesel production

During enzymatic transesterification of soybean oils with methanol for biodiesel production, it was supposed that the maximum biodiesel yield was only 66% since lipozyme TL was a typical lipase with a strict 1,3-positional specificity. However, it has been observed that over 90% biodiesel yield could be obtained. It was therefore assumed, and subsequently demonstrated, that acyl migration occurred during the reaction process. Different factors which may influence the acyl migration were explored further and it has been found that the silica gel acting as the immobilized material contributes significantly to the promotion of acyl migration in the transesterification process. The final biodiesel yield was only 66% when 4% lipozyme TL used, while about 90% biodiesel yield could be achieved when combining 6% silica gel with 4% lipozyme TL, almost as high as that of 10% immobilized lipase used for the reaction.     

Production of biodiesel and lactic acid from rapeseed oil using sodium silicate as catalyst

Biodiesel and lactic acid from rapeseed oil was produced using sodium silicate as catalyst. The transesterification in the presence of the catalyst proceeded with a maximum yield of 99.6% under optimized conditions [3% (w/w) sodium silicate, methanol/oil molar ratio 9/1, reaction time 60 min, reaction temperature 60 °C, and stirring rate 250 rpm]. After six consecutive transesterification reactions, the catalyst was collected and used for catalysis of the conversion of glycerol to lactic acid. A maximum yield of 80.5% was achieved when the reaction was carried out at a temperature of 300 °C for 90 min. Thus, sodium silicate is an effective catalyst for transesterification and lactic acid production from the biodiesel by-product, glycerol.     

Preparation,application, and optimization of Zn/Al complex oxides for biodiesel production under sub-critical conditions

Biodiesel produced by transesterification is a promising green fuel in the future. A new heterogeneous catalyst, Zn/Al complex oxide, was prepared for biodiesel production. The results showed that the catalyst derived from a hydrotalcite-like precursor with a zinc/aluminum atom ratio of 3.74:1 and calcined at 450 °C gave the highest conversion of 84.25%. Analysis of XRD, XPS, FI-IF, TG-DTA, BET and alkalinity tests demonstrated that it is the unique structure of hydrotalcite-like compound precursor that gave the catalyst a high alkalinity greater than 11.1. The optimal reaction condition for Zn/Al complex oxide was under methanol sub-critical condition: 200 °C, 2.5 MPa, 1.4% (wt) catalyst dosage, and 24:1 methanol to oil ratio. Under these conditions, the conversion reached 84.25% after 90 min, which was better than Mg/Al complex oxides. The excellent tolerance to water and free fatty acid was exhibited when the oil feed had fewer than 6% FFA or 10% water content with a conversion greater than 80%.     

Simultaneous conversion of free fatty acids and triglycerides to biodiesel by immobilized Aspergillus oryzae expressing Fusarium heterosporum lipase

The presence of high levels of free fatty acids (FFA) in oil is a barrier to one‐step biodiesel production. Undesirable soaps are formed during conventional chemical methods, and enzyme deactivation occurs when enzymatic methods are used. This work investigates an efficient technique to simultaneously convert a mixture of free fatty acids and triglycerides (TAG). A partial soybean hydrolysate containing 73.04% free fatty acids and 24.81% triglycerides was used as a substrate for the enzymatic production of fatty acid methyl ester (FAME). Whole‐cell Candida antarctica lipase B‐expressing Aspergillus oryzae, and Novozym 435 produced only 75.2 and 73.5% FAME, respectively. Fusarium heterosporum lipase‐expressing A. oryzae produced more than 93% FAME in 72 h using three molar equivalents of methanol. FFA and TAG were converted simultaneously in the presence of increasing water content that resulted from esterification. Therefore, F. heterosporum lipase with a noted high level of tolerance of water could be useful in the industrial production of biodiesel from feedstock that has high proportion of free fatty acids.     

Development and quantification of biodiesel production from chicken feather meal as a cost-effective feedstock by using green technology

Increased urbanization and increase in population has led to an increased demand for fuels. The result is the prices of fuels are reaching new heights every day. Using low-cost feedstocks such as rendered animal fats in biodiesel production will reduce biodiesel expenditures. One of the low-cost feedstocks for biodiesel production from poultry feathers. This paper describes a new and environmentally friendly process for developing biodiesel production technology from feather waste produced in poultry industry. Transesterification is one of the well-known processes by which fats and oils are converted into biodiesel. The reaction often makes use of acid/base catalyst. If the material possesses high free fatty acid then acid catalyst gives better results. The data resulted from gas chromatography (GC) revealed these percentages for fatty acid compositions: myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and arachidonic acid. The biodiesel function group was analyzed by using FTIR. This study concluded that the rooster feathers have superior potential to process them into biodiesel than broiler chicken feathers fat because of fatty acid composition values and it has important properties of biodiesel.     

Biodiesel production via transesterification of palm olein using waste mud crab (Scylla serrata) shell as a heterogeneous catalyst

A recent rise in crab aquaculture activities has intensified the generation of waste shells. In the present study, the waste shells were utilized as a source of calcium oxide to transesterify palm olein into methyl esters (biodiesel). Characterization results revealed that the main component of the shell is calcium carbonate which transformed into calcium oxide when activated above 700 °C for 2 h. Parametric studies have been investigated and optimal conditions were found to be methanol/oil mass ratio, 0.5:1; catalyst amount, 5 wt.%; reaction temperature, 65 °C; and a stirring rate of 500 rpm. The waste catalyst performs equally well as laboratory CaO, thus creating another low-cost catalyst source for producing biodiesel. Reusability results confirmed that the prepared catalyst is able to be reemployed up to 11 times. Statistical analysis has been performed using a Central Composite Design to evaluate the contribution and performance of the parameters on biodiesel purity.     

Ethyl ester production by homogeneous alkaline transesterification: influence of the catalyst

In this work, the process for ethyl ester production is studied using refined sunflower oil, and NaOH, KOH, CH₃ONa, and CH₃OK, as catalysts. In all cases, the reaction is carried out in a single reaction step. The best conversion is obtained when the catalyst is either sodium methoxide or potassium methoxide. We found that during the transesterification with ethanol, soap formation is more important than in the case of methanol. The saponification reaction consumes an important fraction of the catalyst. The amount of catalyst consumed by this reaction is 100% in the case of using hydroxides as catalyst (KOH or NaOH), and 25%, and 28% when using CH₃ONa and CH₃OK as catalysts, respectively. Ethanol increases the catalyst solubility in the oil-ethyl ester phase, thus accelerating the saponification reaction.It is possible to obtain high conversions in a one-step reaction, with a total glycerine concentration close to 0.25%.     

Oil extraction from microalgae for biodiesel production

This study examines the performance of supercritical carbon dioxide (SCCO₂) extraction and hexane extraction of lipids from marine Chlorococcum sp. for lab-scale biodiesel production. Even though the strain of Chlorococcum sp. used in this study had a low maximum lipid yield (7.1 wt% to dry biomass), the extracted lipid displayed a suitable fatty acid profile for biodiesel [C18:1 (∼63 wt%), C16:0 (∼19 wt%), C18:2 (∼4 wt%), C16:1 (∼4 wt%), and C18:0 (∼3 wt%)]. For SCCO₂ extraction, decreasing temperature and increasing pressure resulted in increased lipid yields. The mass transfer coefficient (k) for lipid extraction under supercritical conditions was found to increase with fluid dielectric constant as well as fluid density. For hexane extraction, continuous operation with a Soxhlet apparatus and inclusion of isopropanol as a co-solvent enhanced lipid yields. Hexane extraction from either dried microalgal powder or wet microalgal paste obtained comparable lipid yields.     

Effect of several factors on soluble lipase-mediated biodiesel preparation in the biphasic aqueous-oil systems

Biodiesel is increasingly perceived as an important component of solutions to the important current issues of fossil fuel shortages and environmental pollution. Utilization of soluble lipase offers an alternative approach to lipase-catalyzed biodiesel production using immobilized enzyme or whole-cell catalysis. Soluble lipase NS81020, produced by submerged fermentation of genetically modified Aspergillus oryzae microorganism, was first proposed here as the catalyst of biodiesel preparation with oleic acid in the biphasic aqueous-oil systems. The effect factors such as enzyme concentration, water content, temperature, molar ratio of methanol to oil, stirring rate and pH of buffer solution on the esterification rate were investigated systematically. The reaction time could be shortened with the increasing of enzyme concentration as long as the maximum enzyme absorptive capacity on the interface in the biphasic aqueous-oil systems was not achieved. The optimal water content in the biphasic aqueous-oil systems was 10 wt% by oleic acid weight. The reaction rate was enhanced with the increasing molar ratio of methanol to oil, the increasing stirring rate or the decreasing temperature. Although soluble lipase NS81020 had lower activity at pH 10.55, hydroxyl ion conduced to restrain hydrolysis of methyl ester and facilitated the reaction toward the methyl ester formation.