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.     

Preparation of solid acid catalyst from glucose-starch mixture for biodiesel production

The aim of this work is to study the catalyst prepared by glucose-starch mixture. Assessment experiments showed that solid acid behaved the highest esterification activity when glucose and corn powder were mixed at ratio of 1:1, carbonized at 400 °C for 75 min and sulfonated with concentrated H₂SO₄ (98%) at 150 °C for 5 h. The catalyst was characterized by acid activity measurement, XPS, TEM and FT-IR. The results indicated that solid acid composed of CS_0.073O_0.541 has both Lewis acid sites and Broˇnsted acid sites caused by SO₃H and COOH. The conversions of oleic acid esterification and triolein transesterification are 96% and 60%, respectively. Catalyst for biodiesel production from waste cottonseed oil containing high free fatty acid (FFA 55.2 wt.%) afforded the methyl ester yield of about 90% after 12 h. The catalyst deactivated gradually after recycles usage, but it could be regenerated by H₂SO₄ treatment.     

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.     

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.     

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.     

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%.     

Economic assessment of batch biodiesel production processes using homogeneous and heterogeneous alkali catalysts

An economic feasibility study on four batch processes for the production of biodiesel ranging from 1452 tonnes/year (5000 l/day) to 14,520 tonnes/year (50,000 l/day) is conducted. The four processes assessed are the (1) KOH-W process, characterized by a homogeneous KOH catalyst and hot water purification process; (2) KOH-D process, characterized by a homogeneous KOH catalyst and vacuum FAME distillation process; (3) CaO-W process, characterized by a heterogeneous CaO catalyst and hot water purification process; and (4) CaO-D process, characterized by a heterogeneous CaO catalyst and vacuum FAME distillation process. The costs of the waste cooking oil, fixed costs, and manufacturing costs for producing 7260 tonnes/year (25,000 l/day) of biodiesel by means of the four processes are estimated to be $248–256, $194–232, and $584–641 per tonne of biodiesel, respectively. Among the four processes, the manufacturing costs involved in the CaO-W process are the lowest, in the range from 1452 tonnes/year to 14,520 tonnes/year.     

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.     

Biodiesel production using heterogeneous catalysts

The production and use of biodiesel has seen a quantum jump in the recent past due to benefits associated with its ability to mitigate greenhouse gas (GHG). There are large number of commercial plants producing biodiesel by transesterification of vegetable oils and fats based on base catalyzed (caustic) homogeneous transesterification of oils. However, homogeneous process needs steps of glycerol separation, washings, very stringent and extremely low limits of Na, K, glycerides and moisture limits in biodiesel. Heterogeneous catalyzed production of biodiesel has emerged as a preferred route as it is environmentally benign needs no water washing and product separation is much easier. The present report is review of the progress made in development of heterogeneous catalysts suitable for biodiesel production. This review shall help in selection of suitable catalysts and the optimum conditions 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 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.     

Biocatalysis: Towards ever greener biodiesel production

The cost of lipases and the relatively slower reaction rate remain as the major obstacles for enzymatic production of biodiesel as opposed to the conventional chemical processes. This paper reviews the starting oils usually employed in biodiesel production, the processes for transforming them to biodiesel placing particular emphasis on enzymatic transesterification. The pros and cons of the lipase-based process, the key operational variables and the technological alternatives for attenuating lipase deactivation are also discussed. Finally, suggestions are made for future studies, paying particular attention to the use of whole cell immobilization in the production process, as this methodology may reduce both the cost of the biocatalyst and dependence on lipase manufacturers.     

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.     

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.     

Perspectives for biotechnological production of biodiesel and impacts

In recent years, biological ways for biodiesel production have drawn an increasing attention and compared to chemical approaches, lipase-mediated alcoholysis for biodiesel production has many advantages. Currently, there are extensive reports about enzyme-mediated alcoholysis for biodiesel production, and based on the application forms of biocatalyst, the related research can be classified into immobilized lipase, whole cell catalyst, and liquid lipase-mediated alcoholysis for biodiesel production, respectively. This mini-review is focusing on the study of the aforementioned three forms of biocatalyst for biodiesel production, as well as its impacts and prospects.     

A packed bed membrane reactor for production of biodiesel using activated carbon supported catalyst

In this study, a novel continuous reactor has been developed to produce high quality methyl esters (biodiesel) from palm oil. A microporous TiO₂/Al₂O₃ membrane was packed with potassium hydroxide catalyst supported on palm shell activated carbon. The central composite design (CCD) of response surface methodology (RSM) was employed to investigate the effects of reaction temperature, catalyst amount and cross flow circulation velocity on the production of biodiesel in the packed bed membrane reactor. The highest conversion of palm oil to biodiesel in the reactor was obtained at 70 °C employing 157.04 g catalyst per unit volume of the reactor and 0.21 cm/s cross flow circulation velocity. The physical and chemical properties of the produced biodiesel were determined and compared with the standard specifications. High quality palm oil biodiesel was produced by combination of heterogeneous alkali transesterification and separation processes in the packed bed membrane reactor.     

Microwave assisted alkali-catalyzed transesterification of Pongamia pinnata seed oil for biodiesel production

In this study, microwave assisted transesterification of Pongamia pinnata seed oil was carried out for the production of biodiesel. The experiments were carried out using methanol and two alkali catalysts i.e., sodium hydroxide (NaOH) and potassium hydroxide (KOH). The experiments were carried out at 6:1 alcohol/oil molar ratio and 60 °C reaction temperature. The effect of catalyst concentration and reaction time on the yield and quality of biodiesel was studied. The result of the study suggested that 0.5% sodium hydroxide and 1.0% potassium hydroxide catalyst concentration were optimum for biodiesel production from P. pinnata oil under microwave heating. There was a significant reduction in reaction time for microwave induced transesterification as compared to conventional heating.     

Ultra-sonication application in biodiesel production from heterotrophic oleaginous microorganisms

Utilization of microbial oil for biodiesel production has gained growing interest due to the increase in prices and the shortage of the oils and fats traditionally used in biodiesel production. However, it is still in the laboratory study stage due to the high cost of production. Employing organic wastes as raw materials to grow heterotrophic oleaginous microorganisms for further lipid production to produce biodiesel has been predicted to be a promising method for reducing costs. However, there are many obstacles including the low biodegradability of organic wastes, low lipid accumulation capacity of heterotrophic oleaginous microorganisms while using organic wastes, a great dependence on a high-energy consumption approach for biomass harvesting, utilization of toxic organic solvents for lipid extraction, and large amount of methanol required in trans-esterification and in-situ trans-esterifications. Ultra-sonication as a green technology has been extensively utilized to enhance bio-product production from organic wastes. In this article, ultra-sonication applications in biodiesel production steps with heterotrophic oleaginous microorganisms have been reviewed, and its impact, potential, and limitations on the process have been discussed.     

Efficient lipid production with Trichosporon fermentans and its use for biodiesel preparation

Effects of medium components and culture conditions on biomass and lipid production of Trichosporon fermentans were studied. The optimal nitrogen source, carbon source and C/N molar ratio were peptone, glucose and 163, respectively. The favorable initial pH of the medium and temperature were 6.5 and 25 degrees C. Under the optimized conditions, a biomass of 28.1 g/l and a lipid content of 62.4% could be achieved after culture for 7 days, which were much higher than the original values (19.4 g/l and 50.8%) and the results reported by other groups. T. fermentans could grow well in pretreated waste molasses and a lipid yield of 12.8 g/l could be achieved with waste molasses of 15% total sugar concentration (w/v) at pH 6.0, representing the best result with oleaginous microorganisms on agro-industrial residues. Addition of various sugars to the pretreated molasses could efficiently enhance the accumulation of lipid and the lipid content reached as high as above 50%. Similar to vegetable oils, the lipid mainly contains palmitic acid, stearic acid, oleic acid and linoleic acid and the unsaturated fatty acids amount to about 64% of the total fatty acids. The microbial oil with an acid value of 5.6 mg KOH/g was transesterified to biodiesel by base catalysis after removal of free fatty acids and a high methyl ester yield of 92% was obtained.     

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%.