Techno-economic study of different alternatives for biodiesel production

Biodiesel has become an attractive diesel fuel substitute due to its environmental benefits since it can be made from renewable resource. However, the high costs surrounding biodiesel production remains the main problem in making it competitive in the fuel market either as a blend or as a neat fuel. More than 80% of the production cost is associated with the feedstock itself and consequently, efforts are focused on developing technologies capable of using lower-cost feedstocks, such as recycled cooking oils and wastes from animal or vegetable oil processing operations.     

An overview of solid base heterogeneous catalysts for biodiesel production

The alcoholysis process requires high activity catalysts for biodiesel production. Heterogeneous catalysts have been proven to possess highly active nature and are environment-friendly. The present article emphasizes on various types of solid base catalysts that have been used in the recent past for the production of biodiesel by transesterification of oils. The parameters and conditions affecting the transesterification reaction and biodiesel yield have also been mentioned in the article. Heterogeneous catalysts have the capability to be recycled for many runs in the process without greatly abating the biodiesel yield. Also, such catalysts possess noncorrosive nature, thus making the biodiesel safe to be used in engine without any damage. The exploitation of waste materials as catalysts would reduce the overall production cost of biodiesel. Calcium-based catalysts in the reviewed literature have shown promising outcomes for the future use and would make the process economical for large-scale industrial applications.     

生物技术法生产生物柴油的研究进展

介绍了化学酯交换法、酶催化法、全细胞催化法等生产生物柴油的方法。指出了这一领域难以实现商业化的原因,并针对这些问题提出了相应的建议,分析了生物柴油的现状及发展趋势。     

Modeling analysis of membrane reactor for biodiesel production

Recently, membrane reactor technology was used to produce high‐quality biodiesel because of its advantage of simultaneous transesterification and separation. As the transesterification reaction involves two immiscible phases of methanol (MeOH) and oil (TG), a thorough investigation on the membrane reactor for biodiesel production with the consideration of chemical phase equilibrium (CPE) via modeling analysis, was conducted in this study. A mathematical model was developed based on the modified Maxwell‐Stefan model with the incorporation of CPE. The formation of TG rich micelles dispersed in the continuous phase of MeOH was the most important hypothesis in the model development. The preliminary experiment results show that the permeate compositions from the membrane reactor were closely related to CPE of the system, which was highly depending on the MeOH to TG molar ratio. TG free permeate can only be obtained if the continuous phase of MeOH was free from TG and the TG rich micelles were retained by the membrane. The model verification further confirmed the formation of micelles dispersed in the continuous MeOH phase within the feed side of the membrane reactor and the model was able to predict the performance of the membrane reactor for biodiesel production at an acceptable accuracy. © 2012 American Institute of Chemical Engineers AIChE J, 59: 258–271, 2013     

A review of ionic liquids as catalysts for transesterification reactions of biodiesel and glycerol carbonate production

Biodiesel production has been rapidly increasing due to the strong governmental policies and incentives provided leading to an oversupply of its by-product, glycerol. Therefore, finding ways of utilizing glycerol is essential to increase the net energy and sustainability of biodiesel. Ionic liquids have been used successfully as catalyst for both the production of biodiesel and the conversion of glycerol to glycerol carbonate. These catalysts are relatively environmentally friendly as they have the potential to enable sustainable processes. Herein, the prospect of using ionic liquids to catalyze transesterification triglycerides for the production of biodiesel and the conversion of glycerol to glycerol carbonate will be discussed. Elucidation of the reaction mechanism is expected to provide an in-depth understanding of the process with respect to the effects of cation and anion based on the reactions of interest.     

Experimental analysis of lipid extraction and biodiesel production from wastewater sludge

The most promising renewable alternative fuel, biodiesel, is produced from various lipid sources. Primary and secondary sludge of municipal wastewater treatment facilities are potential sources of lipids. In this study, factorial experimental analyses were used to study the influence of different variables on the lipid extraction and biodiesel production from dried municipal primary and secondary sludge (Adelaide Pollution Control Plant, London, ON, Canada). The empirical models were developed for each factorial analysis. The temperature turned out to be the most significant variable for lipid extraction by using methanol and hexane as solvents. Extraction using methanol resulted in a maximum of 14.46 (wt/wt) % and 10.04 (wt/wt) % lipid (on the basis of dry sludge), from the primary and secondary sludge sources respectively. A maximum of 11.16 (wt/wt) % and 3.04 wt/wt% lipid (on the basis of dry sludge) were extracted from the primary and secondary sludge sources, respectively, using hexane as a solvent. The FAME (fatty acid methyl ester) yield of the H₂SO₄ catalyzed esterification–transesterification of the hexane and methanol extracted lipids were 41.25 (wt/wt) % and 38.94(wt/wt) % (on the basis of lipid) for the primary sludge, and 26.89 (wt/wt) % and 30.28 (wt/wt) % (on the basis of lipid) for the secondary sludge. The use of natural zeolite as a dehydrating agent was increased the biodiesel yield by approximately 18 (wt/wt) % (on the basis of lipid). The effect of temperature and time was also investigated for biodiesel production from the lipid of wastewater sludge. The yield and quality of the FAME were determined by gas chromatography.     

Extraction,transesterification and process control in biodiesel production from Jatropha curcas

Biodiesel has gained worldwide popularity as an alternative energy source due to its renewable, non‐toxic, biodegradable and non‐flammable properties. It also has low emission profiles and is environmentally beneficial. Biodiesel can be used either in pure form or blended with conventional petrodiesel in automobiles without any major engine modifications. Various non‐edible and edible oils can be used for the preparation of biodiesel. With no competition with food uses, the use of non‐edible oils as alternative source for engine fuel will be important. Among the non‐edible oils, such as Pongamia, Argemone and Castor, Jatropha curcas has tremendous potential for biodiesel production. J. curcas, growing mainly in tropical and sub‐tropical climates across the developing world, is a multipurpose species with many attributes and considerable potentials. In this article, we review the oil extraction and characterization, the role of different catalysts on transesterification, the current state‐of‐the‐art in biodiesel production, the process control and future potential improvement of biodiesel production from J. curcas.     

Enzymatic transesterification for production of biodiesel using yeast lipases: An overview

Biodiesel has provided an eco-friendly solution to fuel crisis, as it is renewable, biodegradable and a non-toxic fuel that can be easily produced through enzymatic transesterification of vegetable oils and animal fats. Enzymatic production of biodiesel has many advantages over the conventional methods as high yields can be obtained at low reaction temperatures with easy recovery of glycerol. Microbial lipases are powerful biocatalysts for industrial applications including biodiesel production at lower costs due to its potential in hydrolyzing waste industrial materials. Among them, lipases from yeasts, Candida antarctica, Candida rugosa, Cryptococcus sp., Trichosporon asahii and Yarrowia lipolytica are known to catalyze such reactions. Moreover, stepwise addition of methanol in a three step, two step and single step reactions have been developed using yeast lipases to minimize the inhibitory effects of methanol. The latest trend in biodiesel production is the use of whole-cell as biocatalysts, since the process requires no downstream processing of the enzyme. Synthesis of value added products from the byproduct glycerol further reduces the production cost of biodiesel. This review aims at compiling the information on various yeast lipase catalyzed transesterification reactions for greener production of biodiesel.     

Feasibility study of a thermally coupled reactive distillation process for biodiesel production

Biodiesel fuel represents an interesting alternative as a clean and renewable substitute of fossil fuels. A typical biodiesel production process involves the use of a catalyst, which implies high energy consumptions for the separation of the catalyst and the by-products of the reaction, including those of undesirable side reactions (such as the saponification reaction). A recently proposed process involves the use of short-chain alcohols at supercritical conditions, avoiding the use of a catalyst and the occurrence of the saponification reaction. This process requires fewer pieces of equipment than the conventional one, but its high energy requirements and the need of special materials that support the reaction conditions makes the main product, biodiesel fuel, more expensive than petroleum diesel. In this work, a modification of the supercritical process for the production of biodiesel fuel is proposed. Two alternatives are proposed. The process involves the use of either reactive distillation or thermally coupled reactive distillation. Simulations have been carried out by using the Aspen One™ process simulator to demonstrate the feasibility of such alternatives to produce biodiesel with methanol at high pressure conditions. A design method for the thermally coupled system is also proposed. Both systems have been tested and the results indicate favorable energy performance when compared to the original scheme. Furthermore, the thermally coupled system shows lower energy consumptions than the reactive distillation column.     

Ultrasonic-assisted biodiesel production process from palm oil using alkaline earth metal oxides as the heterogeneous catalysts

The ultrasonic-assisted transesterification of palm oil in the presence of alkaline earth metal oxide catalysts (CaO, SrO and BaO) was investigated. Batch process assisted by 20 kHz ultrasonic cavitation was carried out to study the effect of reaction time (10-60 min), alcohol to palm oil molar ratio (3:1-15:1), catalysts loading (0.5-3%) and varying of ultrasonic amplitudes (25-100%). The activities of the catalysts were mainly related to their basic strength. The catalytic activity was in the sequence of CaO < SrO < BaO. At optimum conditions, 60 min was required to achieve 95% yield compared to 2-4 h with conventional stirring. Also, the yields achieved in 60 min increased from 5.5% to 77.3% (CaO), 48.2% to 95.2% (SrO), and 67.3% to 95.2 (BaO). Fifty percentage amplitude of ultrasonic irradiation was deemed the most suitable value and physical changes on the catalysts after the ultrasonic-assisted reaction were successfully elucidated. BaO catalyst underwent relatively more severe activity drop in the catalyst reusability test. Catalysts dissolution was found to be mainly responsible for activity drop of the reused catalysts, especially with BaO catalyst.     

Kinetic and thermodynamic studies on the extraction of bio oil from Chlorella vulgaris and the subsequent biodiesel production

This research article investigates the extraction of bio-oil from Chlorella vulgaris algae which is then subjected to biodiesel production. To evaluate the maximum oil content, four different pretreatment methods and solvent systems were inspected. Among them, maximum oil yield was obtained from ultrasonic pretreated biomass followed by methanol and methyl tertiary butyl ether solvent extraction. Physico-chemical properties of the bio-oil were analyzed as per AOAC Official Methods. The experiments were then designed to determine how variation in different process parameters influences extraction. From these results, kinetic and thermodynamic parameters were also analyzed. The positive values of ΔS and ΔH and the negative value of ΔG indicate that this process is endothermic, irreversible and spontaneous, respectively. The extracted bio-oil was then subjected to acid catalyzed reaction for biodiesel production. A yield of 98.2?wt% biodiesel was obtained at the optimized condition. Fuel properties were analyzed as per ASTM methods.     

Methanol recycling in the production of biodiesel in a membrane reactor

Membrane reactor technology was used to overcome challenges in biodiesel production. The membrane reactor produces a permeate stream which readily phase separates at room temperature into a fatty acid methyl ester (FAME)-rich non-polar phase and a methanol- and glycerol-rich polar phase. To decrease the overall methanol:oil molar ratio in the reaction system, the polar phase was recycled. Three recycle ratios were tested: 100%, 75% and 50%, at the same residence time and operating conditions. The permeate consistently separated to yield a FAME-rich non-polar phase containing a minimum of 85 wt.% FAME (the remainder being methanol) as well as a methanol/glycerol polar phase. At the highest recycle ratio, the FAME concentration ranged from 85.7 to 92.4 wt.% in the FAME-rich non-polar phase. In addition, the overall molar ratio of methanol:oil in the reaction system was significantly decreased to 10:1 while maintaining a FAME production rate of 0.04 kg/min. As a result, a high purity FAME product was produced.     

Optimization of ultrasonic-assisted heterogeneous biodiesel production from palm oil: A response surface methodology approach

The use of ultrasonic processor in the heterogeneous transesterification of palm oil for biodiesel production has been investigated. Response surface methodology was employed to statistically evaluate and optimize the biodiesel production process catalyzed by two alkaline earth metal oxide catalysts i.e. BaO and SrO. SEM, surface analysis, AAS analysis and the Hammett indicator methods were used for characterization of the catalysts. Four different variables including reaction time (10-60 min), alcohol to oil molar ratio (3:1-15:1), catalyst loading (0.5-3.0 wt.%) and ultrasonic amplitude (25-100%) were optimized. Mathematical models were developed and used to predict the behavior of the process. The models were able to accurately predict the biodiesel yield with less than 5% error for both catalysts. The basic strength of the catalysts was the main reason of their high activities. This study confirmed that the ultrasonic significantly improved the process by reducing the reaction time to less than 50 min and the catalyst loading to 2.8 wt.% to achieve biodiesel yields of above 95%. The optimum alcohol to oil ratio was found to be at 9:1 while the best amplitudes were ∼ 70 and ∼ 80% for the BaO and SrO catalysts, respectively.     

An integrated reactive distillation process for biodiesel production

An integrated reactive distillation process for biodiesel production is proposed. The reactive separation process consists of two coupled reactive distillation columns (RDCs) considering the kinetically controlled reactions of esterification of the fatty acids (FFA) and the transesterification of glycerides with methanol, respectively. The conceptual design of the reactive distillation columns was performed through the construction of reactive residue curve maps in terms of elements. The design of the esterification reactive distillation column consisted of one reactive zone loaded with Amberlyst 15 catalyst and for the transesterification reactive column two reactive zones loaded with MgO were used. Intensive simulation of the integrated reactive process considering the complex kinetic expressions and the PC-SAFT EOS was performed using the computational environment of Aspen Plus. The final integrated RD process was able to handle more than 1% wt of fatty acid contents in the vegetable oil. However, results showed that the amount of fatty acids in the vegetable oil feed plays a key role on the performance (energy cost, catalyst load, methanol flow rate) of the integrated esterification–transesterification reactive distillation process.     

膜接触器中乳化液膜脱除Ni2+的研究

研究了以D2EHPA/煤油/HC1形成的微乳液体系在中空纤维膜接触器中萃取NiCl2水溶液中Ni2的过程,考察了D2EHPA和Ni2+浓度、水溶液酸度、两相流速对溶液中Ni2+的萃取率和传质性能的影响.结果表明,用D2EHPA/煤油/HCl形成的微乳液体系能有效萃取NiCl2水溶液中的微量Ni2+,增大微乳液中载体D2EHPA浓度和料液pH都能提高Ni2的萃取率和过程的总质系数,增加料液流速能显著提高Ni2+的萃取率和过程的总质系数,表明过程的传质阻力主要在水溶液相.     

生物柴油制备方法的应用研究进展

生物柴油以其优良的环境友好性和可再生性引起广泛关注,但较高的生产成本是其商业化生产和应用的障碍之一。综述了生物柴油的化学转酯化法和以游离脂肪酶、固定化脂肪酶、全细胞为催化剂的生物转酯化法的工业研究进展,同时还指出了采用生物转酯化法制备生物柴油时面临的一些问题。     

Technical and Economic Analysis of Conventional and Supercritical Transesterification for Biofuel Production

The transesterification process with potassium hydroxide (KOH) catalyst and the methanol supercritical process were evaluated by Aspen HYSYS software. Castor oil and methanol were used as feed and alcohol. In order to accomplish verification, the simulation results were compared to a laboratory research. For economic analysis, these results were transferred to Aspen Economic Analyzer software. Piping and process equipment cost were calculated for the two processes. Additionally, direct and indirect costs of these processes were estimated.     

Conventional and in situ transesterification of castor seed oil for biodiesel production

In the present study, biodiesel production from Ricinus communis L. red and BRS-149 nordestina varieties seed oil is reported. Reactions were made through conventional and in situ processes using ethanol and evaluating the addition of n-hexane as co-solvent. The content of ethyl esters was quantified by ¹H NMR. The highest conversions were obtained from crude oil (conventional reaction) after pre-esterification, using ethanol and a molar ratio of alcohol to oil of 60; furthermore, the addition of n-hexane was not significant on yield. Under these conditions, best conversion was around 95% for both varieties.