Transesterification of palm oil to methyl ester on activated carbon supported calcium oxide catalyst

In this study, methyl ester (ME) was produced by transesterification of palm oil (CPO) (cooking grade) using activated carbon supported calcium oxide as a solid base catalyst (CaO/AC). Response surface methodology (RSM) based on central composite design (CCD) was used to optimize the effect of reaction time, molar ratio of methanol to oil, reaction temperature and catalyst amount on the transesterification process. The optimum condition for CPO transesterification to methyl ester was obtained at 5.5 wt.% catalyst amount, 190 °C temperature, 15:1 methanol to oil molar ratio and 1 h 21 min reaction time. At the optimum condition, the ME content was 80.98%, which is well within the predicted value of the model. Catalyst regeneration studies indicate that the catalyst performance is sustained after two cycles.     

海滨锦葵油制备生物柴油工艺条件优化

以海滨锦葵油为原料制备生物柴油。通过单因素试验及正交试验研究了反应温度、催化剂用量、醇油摩尔比、反应时间、搅拌强度等因素对酯交换率的影响。结果表明,在试验范围内各影响因素对酯交换率作用的大小依次为：搅拌强度＞催化剂用量＞醇油摩尔比＞反应时间＞反应温度。海滨锦葵油制备生物柴油的最佳工艺参数为：搅拌强度为1800r.min-1,催化剂KOH用量为海滨锦葵油质量的1%,醇油摩尔比6/1,反应时间60min,反应温度65℃,在该工艺条件下,酯交换反应三次,酯交换率达到97.8%。     

Soybean oil methyl esters preparation using NaX zeolites loaded with KOH as a heterogeneous catalyst

The transesterification of soybean oil with methanol to methyl esters was carried out using NaX zeolites loaded with KOH as a solid base catalyst. Best result was obtained with NaX zeolite loaded with 10% KOH, followed by heating at 393 K for 3 h. When the transesterification reaction was carried out at reflux of methanol (338 K), with a 10:1 molar ratio of methanol to soybean oil, a reaction time of 8 h and a catalyst amount of 3 wt.%, the conversion of soybean oil was 85.6%.     

Direct preparation of biodiesel from rapeseed oil leached by two-phase solvent extraction

A new method which coupled the two-phase solvent extraction (TSE) with the synthesis of biodiesel was studied. Investigations were carried out on transesterification of methanol with oil-hexane solution coming from TSE process in the presence of sodium hydroxide as the catalyst. Biodiesel (fatty acid methyl esters) were the products of transesterification. The influential factors of transesterification, such as reaction time, catalyst concentration, mole ratio of methanol to oil and reaction temperature were optimized. The results showed that the optimal reaction parameters were sodium hydroxide concentration 1.1% by weight of rapeseed oil, mole ratio of methanol to oil 9:1, reaction time 120 min, and reaction temperature 55-60 degrees C. Under these conditions, the TG conversion would rise up to 98.2%. Based on the new method, biodiesel production process could be simplified and the biodiesel cost could be reduced.     

Process optimization for biodiesel production from mahua (Madhuca indica) oil using response surface methodology

A central composite rotatable design was used to study the effect of methanol quantity, acid concentration and reaction time on the reduction of free fatty acids content of mahua oil during its pretreatment for making biodiesel. All the three variables significantly affected the acid value of the product, methanol being the most effective followed by reaction time and acid catalyst concentration. Using response surface methodology, a quadratic polynomial equation was obtained for acid value by multiple regression analysis. Verification experiments confirmed the validity of the predicted model. The optimum combinations for reducing the acid level of mahua oil to less than 1% after pretreatment was 0.32 v/v methanol-to-oil ratio, 1.24% v/v H2SO4 catalyst and 1.26 h reaction time at 60 degrees C. After the pretreatment of mahua oil, transesterification reaction was carried out with 0.25 v/v methanol-to-oil ratio (6:1 molar ratio) and 0.7% w/v KOH as an alkaline catalyst to produce biodiesel. The fuel properties of mahua biodiesel so obtained complied the requirements of both the American and European standards for biodiesel.     

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.     

Biodiesel production from high acid value waste frying oil catalyzed by superacid heteropolyacid

Transesterification of waste cooking oil with high acid value and high water contents using heteropolyacid H3PW12O40 x 6H2O (PW12) as catalyst was investigated. The hexahydrate form of PW(12) was found to be the most promising catalyst which exhibited highest ester yield 87% for transesterification of waste cooking oil and ester yield 97% for esterification of long-chain palmitic acid, respectively. The PW12 acid catalyst shows higher activity under the optimized reaction conditions compared with conventional homogeneous catalyst sulfuric acid, and can easily be separated from the products by distillation of the excess methanol and can be reused more times. The most important feature of this catalyst is that the catalytic activity is not affected by the content of free fatty acids (FFAs) and the content of water in the waste cooking oil and the transesterification can occur at a lower temperature (65 degrees C), a lower methanol oil ratio (70:1) and be finished within a shorter time. The results illustrate that PW12 acid is an excellent water-tolerant and environmentally benign acid catalyst for production of biodiesel from waste cooking oil.     

Ultrasonic monitoring of glycerol settling during transesterification of soybean oil

A low-intensity ultrasonic measurement system was used to monitor the products of transesterification of soybean oil in methanol to FAME (biodiesel). The byproducts of the transesterification reaction are methyl esters, glycerol and other products. During the transesterification reaction, the glycerol, having a higher density than the methyl ester, settles at the bottom of the reaction vessel. The aim of this study was to measure the glycerol deposition rate during transesterification and to assess the reaction rate and end time. Soybean oil was converted into biodiesel at four temperature levels. The amount of catalyst (KOH) used in the transesterification reactions was determined by titration. The ultrasonic waveforms captured during the reaction were recorded and analyzed automatically. The ultrasonic system monitored the effects of reaction temperatures on the glycerol settling rate and the reaction end times. The ultrasonic measurement of glycerol settling would be a useful non-destructive method for evaluating the effects of parameters such as catalyst amount, mixing time and temperature on transesterification reactions.     

K_2CO_3/γ-Al_2O_3催化棕榈油和甲醇酯交换反应制备生物柴油

采用浸渍法制备K2CO3/γ-Al2O3负载型固体碱催化剂,用X线衍射(XRD)和热质量分析法(DSC-TGA)表征催化剂的物化性质,考察催化剂在棕榈油和甲醇酯交换制备生物柴油中的反应性能。结果表明:活性组分已成功负载到载体γ-Al2O3上,且在高温焙烧过程中K2CO3和γ-Al2O3之间产生了相互作用;在K2CO3负载量22.6%、醇油摩尔比12∶1、反应时间3h、催化剂质量分数3%、反应温度65℃的条件下,甲酯产率最高可达91.6%。     

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.     

The effect of the acidity of rapeseed oil on its transesterification

The aim of this work is to study the transesterification of vegetable oil with a high acid number at unchanged reaction conditions. Rapeseed oil was used as the raw material and its acid number was changed by the addition of oleic acid (from 0.89 to 12.25 mg KOH/g). Methanol was used for transesterification (molar ratio of oil to methanol 1:6) and potassium hydroxide was used as a catalyst. After the reaction time, the residue of the catalyst was neutralised by gaseous carbon dioxide and the methanol excess was removed. After the separation of two phases, each of them was analyzed (in the ester phase: yield, content of methyl ester and acid number; in the glycerol phase: yield, density, viscosity, content of glycerol, soaps, methyl ester, potassium carbonate and hydrogen carbonate). The obtained data was compared with theoretical material balances and the effect on the saponification of oil was discussed. The results show that the yield of methyl ester (biodiesel) is significantly affected by a higher acid number, as well as enhanced soap formation. On the other hand, the conversion of the oil and acid number of the ester phase remain at constant values in studied borders.     

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.     

Catalytic Packed-Bed Reactor Configuration for Biodiesel Production Using Waste Oil as Feedstock

Pumice, a natural porous silica material, exchanged with potassium is an efficient heterogeneous particulate catalytic material for triglycerides and free fatty acids transesterification reaction from sunflower oil and waste frying oil at low temperature. In this work, a packed-bed catalytic configuration reactor using this catalytic material was developed for biodiesel fuel production from sunflower oil and frying oil feedstock. Reactor operation variables as methanol/oil molar ratio, catalyst amount, reaction time, and reaction temperature were studied. Results were compared with those obtained from the same transesterification reaction proceeding in a slurry batch reactor. The packed-bed catalytic reactor configuration can be useful in order to minimize catalyst mechanical damage occurring in the slurry reactor due to continuous stirring. The possibility of using a packed-bed reactor shows some advantages because the catalyst stays confined in the reactor bed and the reaction products can be easily separated, besides the mechanical stability of the catalyst particles is achieved.     

Optimization of microwave-assisted transesterification of dry algal biomass using response surface methodology

The effect of microwave irradiation on the simultaneous extraction and transesterification (in situ transesterification) of dry algal biomass to biodiesel was investigated. A high degree of oil/lipid extraction from dry algal biomass and an efficient conversion of the oils/lipids to biodiesel were demonstrated in a set of well-designed experimental runs. A response surface methodology (RSM) was used to analyze the influence of the process variables (dry algae to methanol (wt/vol) ratio, catalyst concentration, and reaction time) on the fatty acid methyl ester conversion. Based on the experimental results and RSM analysis, the optimal conditions for this process were determined as: dry algae to methanol (wt/vol) ratio of around 1:12, catalyst concentration about 2 wt.%, and reaction time of 4 min. The algal biodiesel samples were analyzed with GC-MS and thin layer chromatography (TLC) methods. Transmission electron microscopy (TEM) images of the algal biomass samples before and after the extraction/transesterification reaction are also presented.     

Influence of vegetable oils fatty-acid composition on biodiesel optimization

Biodiesel is an alternative fuel for diesel engines produced through transesterification of oleaginous feedstocks. To analyze the influence of the fatty-acid composition on biodiesel optimization, transesterification of several vegetable oils has been studied. Reactions were carried out in flasks filled with vegetable oils, heated to the reaction temperature and stirred at 1100 rpm. The reactions started when the methanol and potassium hydroxide solutions were added to the flasks. Concentration of catalyst, amount of methanol, reaction temperature and time were optimized using a factorial design and a surface response design. Also, a kinetics study was carried out to optimize the reaction time. Results showed that reaction parameters optimal values depend on the oil chemical and physical properties. It can be concluded from this field trial that the effect of both catalyst concentration and reaction time over the transesterification yield is greatly influenced by the saturation degree and fatty-acid chain length.     

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).     

Biodiesel production using a membrane reactor

The immiscibility of canola oil in methanol provides a mass-transfer challenge in the early stages of the transesterification of canola oil in the production of fatty acid methyl esters (FAME or biodiesel). To overcome or rather, exploit this situation, a two-phase membrane reactor was developed to produce FAME from canola oil and methanol. The transesterification of canola oil was performed via both acid- or base-catalysis. Runs were performed in the membrane reactor in semi-batch mode at 60, 65 and 70 degrees C and at different catalyst concentrations and feed flow rates. Increases in temperature, catalyst concentration and feedstock (methanol/oil) flow rate significantly increased the conversion of oil to biodiesel. The novel reactor enabled the separation of reaction products (FAME/glycerol in methanol) from the original canola oil feed. The two-phase membrane reactor was particularly useful in removing unreacted canola oil from the FAME product yielding high purity biodiesel and shifting the reaction equilibrium to the product side.     

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.     

Biodiesel production and optimization from Calophyllum inophyllum linn oil (honne oil) – A three stage method

The present work examines the production of a biodiesel from a non-edible oil namely honne oil (Calophyllum inophyllum linn). A three stage process viz., pre-treatment, alkali catalyzed transesterification and post treatment adopted for the production is discussed. The reaction parameters such as methanol to oil molar ratio, catalyst concentration, temperature and time have been optimized for the production of biodiesel. The yield of biodiesel from the honne oil under the optimized conditions is found to be 89%.     

Synthesis of fatty acid methyl ester from palm oil (Elaeis guineensis) with Ky(MgCa)2xO3 as heterogeneous catalyst

Fatty acid methyl esters (FAME) were produced from palm oil using eggshell modified with magnesium and potassium nitrates to form a composite, low-cost heterogeneous catalyst for transesterification. The catalyst, prepared by the combination of impregnation/co-precipitation was calcined at 830 °C for 4 h. Transesterification was conducted at a constant temperature of 65 °C in a batch reactor. Design of experiment (DOE) was used to optimize the reaction parameters, and the conditions that gave highest yield of FAME (85.8%) was 5.35 wt.% catalyst loading at 4.5 h with 16:1 methanol/oil molar ratio. The results revealed that eggshell, a solid waste, can be utilized as low-cost catalyst after modification with magnesium and potassium nitrates for biodiesel production.