The influence of free fatty acid intermediate on biodiesel production from soybean oil by whole cell biocatalyst

The whole cell of lipase-producing Rhizopus oryzae was employed as biocatalyst for transesterification of soybean oil containing oleic acid. The free fatty acid (FFA) intermediate, playing an important role in the kinetics of transesterification of soybean oil, was thoroughly investigated and characterized. The conversion was more than 97% at the initial FFA content of 5.5%. A high content of FFA could protect the lipase from denaturation. The 34.6 percent of FFA with the optimal 26-mg mL⁻¹ methanol resulted in a specific reaction rate of 420 mg h⁻¹g-dry cell⁻¹. In addition, the methanol/FFA ratio at 0.83-1.7 provides a good indication of the fatty acid methyl esters conversions for different initial FFA contents. In the transesterification process, more FFA intermediate present would become beneficial to conversion of retrograde feedstock to biodiesel. The immediately generated and original FFA content become the major rate-determining factor in the FFA-mixed transesterification process.     

Optimization of conversion of waste rapeseed oil with high FFA to biodiesel using response surface methodology

In the present study, waste rapeseed oil with high free fatty acids (FFA) was used as feedstock for producing biodiesel. In the pretreatment step, FFA was reduced by distillation refining method. Then, biodiesel was produced by alkaline-catalyzed transesterification process, which was designed according to the 2⁴ full-factorial central composite design. The response surface methodology (RSM) was used to optimize the conditions for the maximum conversion to biodiesel and understand the significance and interaction of the factors affecting the biodiesel production. The results showed that catalyst concentration and reaction time were the limiting conditions and little variation in their value would alter the conversion. At the same time, there was a significant mutual interaction between catalyst concentration and reaction time.The biodiesel produced in the present experiment was analyzed by gas chromatography/mass spectrometry (GC/MS), which showed that it mainly contained six fatty acid methyl esters. In addition, the diesel indexes analysis showed that most of the fuel properties were in reasonable agreement with the 0# diesel standard of China (GB252-2000) and the biodiesel standard of America (ASTM D6751).     

Synthesis of biodiesel from waste vegetable oil with large amounts of free fatty acids using a carbon-based solid acid catalyst

A carbon-based solid acid catalyst was prepared by the sulfonation of carbonized vegetable oil asphalt. This catalyst was employed to simultaneously catalyze esterification and transesterification to synthesis biodiesel when a waste vegetable oil with large amounts of free fatty acids (FFAs) was used as feedstock. The physical and chemical properties of this catalyst were characterized by a variety of techniques. The maximum conversion of triglyceride and FFA reached 80.5 wt.% and 94.8 wt.% after 4.5 h at 220 °C, when using a 16.8 M ratio of methanol to oil and 0.2 wt.% of catalyst to oil. The high catalytic activity and stability of this catalyst was related to its high acid site density (–OH, Brönsted acid sites), hydrophobicity that prevented the hydration of –OH species, hydrophilic functional groups (–SO₃H) that gave improved accessibility of methanol to the triglyceride and FFAs, and large pores that provided more acid sites for the reactants.     

催化合成生物柴油的双金属络合物固体催化剂

制备了基于亚铁氰化锌的双金属氰化物络合物(DMC),可一步同时催化酯交换和酯化反应制备生物柴油,该催化剂体系具有不受水毒性影响的特点。用3wt%的DMC催化剂在433K,醇油摩尔比为16∶1以及水和脂肪酸含量各10wt%的条件下分别同时催化甘油三酯、脂肪酸和甲醇的酯交换、酯化反应,生物柴油产率可达98%以上。对催化剂进行X射线衍射、热重红外联用分析、元素分析、比表面积和孔体积测定、扫描电镜等手段表征,结果表明:该催化剂为晶态与非晶态组分混合结构,其表面晶态决定其在高水含量、高酸值的环境下仍具有较好的催化活性,验证得出活性位点可能为锌离子。     

Heterogeneous catalysis for biodiesel production from Jatropha curcas oil (JCO)

This work focuses on the development of heterogeneous catalysts for biodiesel production from high free fatty acid (FFA) containing Jatropha curcas oil (JCO). Solid base and acid catalysts were prepared and tested for transesterification in a batch reactor under mild reaction conditions. Mixtures of solid base and acid catalysts were also tested for single-step simultaneous esterification and transesterification. More soap formation was found to be the main problem for calcium oxide (CaO) and lithium doped calcium oxide (Li-CaO) catalysts during the reaction of jatropha oil and methanol than for the rapeseed oil (RSO). CaO with Li doping showed increased conversion to biodiesel than bare CaO as a catalyst. La₂O₃/ZnO, La₂O₃/Al₂O₃ and La_0.1Ca_0.9MnO₃ catalysts were also tested and among them La₂O₃-ZnO showed higher activity. Mixture of solid base catalysts (CaO and Li-CaO) and solid acid catalyst (Fe₂(SO₄)₃) were found to give complete conversion to biodiesel in a single-step simultaneous esterification and transesterification process.     

Production of biodiesel from castor oil using iron (II) doped zinc oxide nanocatalyst

The depletion of fossil fuels has caused the price of petroleum to rise remarkably and created need for alternative energy such as biodiesel. In the present study, the biodiesel was produced from castor oil using ferromagnetic zinc oxide nanocomposite as heterogeneous catalyst for transesterification reaction. Single phase of nanocatalyst were confirmed by X-Ray Diffraction analysis. The spherical shape of the aggregated nanocatalyst was observed in Scanning Electron Microscopy. Magnetic properties were analysed using vibrating sample magnetometer. Atomic Force Microscopic analysis revealed the larger surface area and roughness of nanocatalyst. The biodiesel yield of 91% (w/w) was obtained in 50 min at 55 °C with 14 wt % catalyst loading and 12:1 methanol/oil ratio and was confirmed by Gas chromatograph with Mass Spectrometer. The result showed that the iron (II) doped ZnO nanocatalyst is a promising catalyst for the production of biodiesel via heterogeneous catalytic transesterification under milder reaction conditions.     

Biodiesel Production Facilities from Vegetable Oils and Animal Fats

Abstract

Biodiesel is a renewable fuel that can be produced from vegetable oils, animal fats, and used cooking oil including triglycerides. Biodiesel, an alternative biodegradable diesel fuel, is derived from triglycerides by transesterification with methanol and ethanol. Concerns about the depletion of diesel fuel reserves and the pollution caused by continuously increasing energy demands make biodiesel an attractive alternative motor fuel for compression ignition engines. There are four different ways of modifying vegetable oils and fats to use them as diesel fuel, such as pyrolysis (thermal cracking), dilution with hydrocarbons (blending), emulsification and transesterification. The most commonly used process is transesterification of vegetable oils and animal fats. The transesterification reaction is affected by molar ratio of glycerides to alcohol, catalysts, reaction temperature, reaction time and free fatty acids and water content of oils or fats. In the transesterification, free fatty acids and water always produce negative effects, since the presence of free fatty acids and water causes soap formation, consumes catalyst and reduces catalyst effectiveness, all of which result in a low conversion. Biodiesel has over double the price of diesel. The high price of biodiesel is in large part due to the high price of the feedstock.     

Studies on the performance of tubular flow reactor for esterification of free fatty acid from used cooking oil using highly porous cation exchange resin as catalyst

Semi-batch esterification of free fatty acid (FFA) from used cooking oil with methanol was carried out using RCP160M cation exchange resin in a tubular flow reactor (TFR). The results revealed that the conversion of FFA increased with the increase of catalyst bed height, methanol to oil mass ratio and decreases with increase of feedstock flow rates. However, the FFA conversion was decreased upon further increases of methanol to oil mass ratio from 6:1 to 12:1. This might possibly happen due to several factors such as mass transfer limitation between reactants and catalyst and inhomogeneity of the reactants during the reaction.     

Transesterification of crude Jatropha oil by activated carbon-supported heteropolyacid catalyst in an ultrasound-assisted reactor system

Transesterification of crude Jatropha oil in presence of tungstophosphoric acid (TPA) supported on activated carbon (AC) using ultrasound-assisted process was investigated. The generated catalysts were characterized for physical and chemical properties to examine the effects of different TPA loadings (15%, 20%, 25% w/w). The catalysts were then used in the transesterification of Jatropha oil with high free fatty acid content. The catalyst with 20% TPA loading achieved the best methyl ester yield, achieving 87.33% in just 40 min. The quality of the feed stock was varied by increasing the water content and FFA content to test the tolerance of the catalysts towards these parameters separately. The catalyst showed good water tolerance to a limit of 1% w/w and proven to be insensitive to the increment of FFA in the feed stock. The catalyst was also investigated for possible reusability and TPA leaching under ultrasonic conditions.     

High free fatty acid coconut oil as a potential feedstock for biodiesel production in Thailand

Coconut oil having 12.8% free fatty acid (FFA) was used as a feedstock to produce biodiesel by a two-step process. In the first step, FFA level of the coconut oil was reduced to 0.6% by acid-catalyzed esterification. In the second step, triglycerides in product from the first step were transesterified with methanol by using an alkaline catalyst to produce methyl esters and glycerol. Effect of parameters related to these processes was studied and optimized, including methanol-to-oil ratio, catalyst concentration, reaction temperature, and reaction time. Methyl ester content of the coconut biodiesel was determined by GC to be 98.4% under the optimum condition. The viscosity of coconut biodiesel product was very close to that of Thai petroleum diesel and other measured properties met the Thai biodiesel (B100) specification.     

In situ reactive extraction of Jatropha curcas L. seeds assisted by ultrasound: Preliminary studies

Esterification is required to reduce the high free fatty acid (FFA) content of crude Jatropha oil to below 3% prior to transesterification. In this study, raw decorticated Jatropha seeds were employed as the feedstock in in situ reactive extraction assisted by ultrasound in the presence of sulfuric acid (H₂SO₄) as a catalyst. Extraction efficiency, esterification efficiency, and fatty acid methyl ester (FAME) yield were optimized as a function of ultrasonic pulse mode, amplitude, and H₂SO₄ amount. The optimum extraction efficiency of 83.96%, esterification efficiency of 71.10%, and FAME yield of 38.58% were achieved at a pulse mode of 5 s on/2 s off, an ultrasonic amplitude of 60%, and an H₂SO₄ amount of 5 mL in reaction time of 150 min.     

Biodiesel production from mixture of mahua and simarouba oils with high free fatty acids

A suitable process comprising acid pretreatment followed by main base transesterification reaction was developed to produce biodiesel from mixture of Mahua (M) and Simarouba (S) oils with high free fatty acids (FFA). The acid pretreatment reduced the high FFAs of the mixture of oils to around 1% which were then transesterified with methanol and KOH as catalyst at a reaction temperature of 60 °C. A genetic algorithm coupled with artificial neural network (ANN-GA) model to obtain the best pretreatment process parameters for bringing down the FFA level of individual vegetable oils to around 1% was modified to include the wide range of oils and validated for mixtures of M and S oils. The quality of biodiesel produced was analyzed by gas chromatography (GC), which indicated above 90% ester conversion. The fuel properties of biodiesel were found to be comparable to diesel and were conforming to the latest biodiesel standards.     

Production of ethyl ester from esterified crude palm oil by microwave with dry washing by bleaching earth

The production of ethyl ester from a feed material of esterified crude palm oil with 1.7 wt% of free fatty acid (FFA) content using microwave heating was investigated. Parametric studies were carried out to investigate the optimum conditions for the transesterification process (amount of ethanol, amount of catalyst and reaction time). As a result, optimum reaction parameters for the transesterification process aided by microwave heating have been identified: a molar ratio of oil to ethanol of 1:8.5, 1.5 wt% of KOH/oil, a reaction time of 5 min and a microwave power of 70 W. Glycerin from the ester phase was separated by adding 10 wt% of pure glycerin. The ethyl ester was purified with 1.2 wt% of bleaching earth to remove the residual catalyst and residual glycerin. This transesterification process provided a yield of 85 wt% with an ester content of 98.1 wt%. The final ethyl ester product met the specifications stipulated by ASTM D6751-02.     

Biodiesel production using gel‐type cation exchange resin at different ionic forms

In this study, a strong acidic‐type cation exchange resin was used in the transesterification of corn oil to fatty acid methyl esters (FAME). The gel‐type cation exchange resin (Purolite‐PD206) was used in H⁺ and Na⁺ forms to utilize ion‐exchange resin as effective heterogeneous catalyst in the production of biodiesel. Effect of ionic forms of ion exchange resin on free fatty acid (FFA) conversion and composition was investigated by using different amounts of ion exchange resin (12, 16, and 20 wt%), various mole ratios of methanol to oil (1:6, 1:12, and 1:18 mol/mol), reaction temperatures (63, 65, and 67°C), and reaction time (24, 36, and 48 h) during transesterification reaction. The highest FFA conversions of 73.5% and 79.45% were obtained at conditions of 20 wt% of catalyst, 65°C of reaction temperature, 18:1 as methanol to oil ratio, and 48 h of reaction time for H⁺ and Na⁺ forms of ion exchange resin, respectively. These results were obtained from regression equations established by using analysis of variance (ANOVA) model according to the experimental results of selected parameters. Gas chromatography analysis revealed that FAME is mainly composed of C16:0 (palmitic), C18:1 (oleic), and C18:2 (linoleic) acids of methyl ester.     

Biodiesel production from degummed Jatropha curcas oil using constant-temperature ultrasonic water bath

This paper studied tri-basic potassium phosphate for transesterification process with degummed crude Jatropha curcas oil using constant-temperature, ultrasonic water bath generating low-intensity pulses with good energy distribution converting the maximum amount of biodiesel. Tri-basic potassium phosphate is suitable for J. curcas oil when the free fatty acid (FFA) content is less than 2%. The optimal reaction levels are catalyst 1.0 wt%, temperature of 50°C, and methanol-to-oil molar ratio of 12:1. The yield is 98% after 45 min, at 20 kHz frequency. The catalytic activity is found similar to potassium hydroxide and the catalyst solubility is only 4.27 ppm.     

Lithium ion impregnated calcium oxide as nano catalyst for the biodiesel production from karanja and jatropha oils

Lithium impregnated calcium oxide has been prepared by wet impregnation method in nano particle form as supported by powder X-ray diffraction and transmission electron microscopy. Basic strength of the same was measured by Hammett indicators. Calcium oxide impregnated with 1.75 wt% of lithium was used as solid catalyst for the transesterification karanja and jatropha oil, containing 3.4 and 8.3 wt% of free fatty acids, respectively. The reaction parameters, viz., reaction temperature, alcohol to oil molar ratio, free fatty acid contents, amount of catalyst and amount of impregnated lithium ion in calcium oxide support, have been studied to establish the most suitable condition for the transesterification reaction. The complete transesterification of karanja and jatropha oils was achieved in 1 and 2 h, respectively, at 65 °C, utilizing 12:1 molar ratio of methanol to oil and 5 wt% (catalyst/oil, w/w) of catalyst. Few physicochemical properties of the prepared biodiesel samples have been studied and compared with standard values.     

Biodiesel production over copper vanadium phosphate

In the present study, copper vanadium phosphate (CuVOP) with three-dimensional network structure was synthesized by hydrothermal method, and was characterized by Infrared spectrum (IR), elemental analysis (EA), EDXRF (energy dispersive X ray fluorescence) etc. Moreover, soybean oil was used as feedstock for producing biodiesel, and biodiesel was produced by CuVOP-catalyzed transesterification process. Response surface methodology was employed to statistically evaluate and optimize the conditions for the maximum conversion to biodiesel, and the effects of amount of catalyst, ratio of methanol to oil, reaction time and reaction temperature were investigated by the 2⁴ full-factorial central composite design. The maximum conversion is obtained at amount of catalyst of 1.5%, methanol/oil molar ratio of 6.75, reaction temperature of 65 °C and reaction time of 5 h. Copper vanadium phosphate CuVOP resulted very active in the transesterification reaction for biodiesel production.     

Calcium-based mixed oxide catalysts for methanolysis of Jatropha curcas oil to biodiesel

Calcium-based mixed oxides catalysts (CaMgO and CaZnO) have been investigated for the transesterification of Jatropha curcas oil (JCO) with methanol, in order to evaluate their potential as heterogeneous catalysts for biodiesel production. Both CaMgO and CaZnO catalysts were prepared by coprecipitation method of the corresponding mixed metal nitrate solution in the presence of a soluble carbonate salt at ∼ pH 8-9. The catalysts were characterized by X-ray diffraction (XRD), temperature programmed desorption of CO₂ (CO₂-TPD), scanning electron microscopy (SEM) and N₂ adsorption (BET). The conversion of JCO by CaMgO and CaZnO were studied and compared with calcium oxide (CaO), magnesium oxide (MgO) and zinc oxide (ZnO) catalysts. Both CaMgO and CaZnO catalysts showed high activity as CaO and were easily separated from the product. CaMgO was found more active than CaZnO in the transesterification of JCO with methanol. Under the suitable transesterification conditions at 338 K (catalyst amount = 4 wt. %, methanol/oil molar ratio = 15, reaction time = 6 h), the JCO conversion of more than 80% can be achieved over CaMgO and CaZnO catalysts. Even though CaO gave the highest activity, the conversion of JCO decreased significantly after reused for forth run whereas the conversion was only slightly lowered for CaMgO and CaZnO after sixth run.     

Effect of feedstocks and chain length of alcohols on whole-cell-catalyzed generation of alkyl esters

The dried biomass of a whole-cell catalyst was used for the generation of alkyl esters from cottonseed oil and acid oil with different alcohols (methanol to decanol) as acyl acceptors. The conversion of alkyl esters increased from methanol (12%) to pentanol (96%), followed by decreased from hexanol (86%) to decanol (64%) in case of acid oil. The extent of transesterification was significantly higher (P < 0.01) in case of acid oil, with most of the acyl acceptors as compared to cottonseed oil. The study demonstrates the use of dried biomass of fungus as catalyst and an effective feedstock such as acid oil, for the generation of various industrially important alkyl esters.     

Production and evaluation of biodiesel from mixed castor oil and waste chicken oil

Biodiesel was developed from an unconventional feedstock, i.e. an equivalent blend of castor bean and waste chicken oil through the alkaline-catalyzed transesterification with methanol. The process variables including the alkaline catalyst concentration, methanol to oil molar ratio, reaction temperature, reaction time, and the alkaline catalyst type were investigated. The highest yield of biodiesel (97.20 % ~ 96.98 % w/w ester content) was obtained under optimum conditions of 0.75 % w/w of oil, 8:1 methanol to oil molar ratio, 60°C temperature, and a duration of 30 min. Properties of the produced biodiesel satisfied those specified by the ASTM standards. The results thus indicated that the suggested blend oils are suitable feedstock for the production of biodiesel. The process was found to follow pseudo first-order kinetics, and the activation energy was found to be 8.85 KJ/mole.