Palm oil transesterification in sub- and supercritical methanol with heterogeneous base catalyst

An environmentally benign process for the production of methyl ester using γ-alumina supported heterogeneous base catalyst in sub- and supercritical methanol has been developed. The production of methyl ester in refluxed methanol conventionally utilized double promoted γ-alumina heterogeneous base catalyst (CaO/KI/γ-alumina); however, this process requires a large amount of catalyst and a long reaction time to produce a high yield of methyl ester. This study carries out methyl ester production in sub- and supercritical methanol with the introduction of an optimized catalyst used in the previous work for the purpose of improving the process and enhancing efficiency. CaO/KI/γ-Al₂O₃ catalyst was prepared by precipitation and impregnation methods. The effects of catalyst amount, reaction temperature, reaction time, and the ratio of oil to methanol on the yield of biodiesel ester were studied. The reaction was carried out in a batch reactor (8.8 ml capacity, stainless steel, AKICO, Japan). Results show that the use of CaO/KI/γ-Al₂O₃ catalyst effectively reduces both reaction time and required catalyst amount. The optimum process conditions were at a temperature of 290 °C, ratio of oil to methanol of 1:24, and a catalyst amount of 3% over 60 min of reaction time. The highest yield of biodiesel obtained under these optimum conditions was almost 95%.     

Effect of mixed alcohol reactants on ultrasonic alcoholysis of canola oil

The effect of ultrasonic irradiation energy was analyzed according to the kinds of alcohol in the ultrasonic alcoholysis. The ultrasonic irradiation energy density of ethanol (792.9 kJ/L) is higher than methanol (649.8 kJ/L). The optimum mixing ratio of canola oil, methanol and ethanol was proven as 1, 5 and 1, respectively. Also the optimum reaction conditions for the ultrasonic alcoholysis were a reaction temperature of 60 °C, ultrasonic irradiation power of 500 W, reaction time of 50 min, and alkaline catalyst (KOH) content of 0.6 wt.%. From these results, the optimum alcohol mixing ratio and the optimum process conditions were determined, with good quality biodiesel being manufactured.     

Dolomite as a heterogeneous catalyst for transesterification of canola oil

In this study, the catalytic activity of dolomite was evaluated for the transesterification of canola oil with methanol to biodiesel in a heterogeneous system. The influence of the calcination temperature of the catalyst and the reaction variables such as the temperature, catalyst amount, methanol/canola oil molar ratio, and time in biodiesel production were investigated. The maximum activity was obtained with the catalyst calcined at 850 °C. When the reaction was carried out at reflux of methanol, with a 6:1 molar ratio of methanol to canola oil and a catalyst amount of 3 wt.% the highest FAME yield of 91.78% was obtained after 3 h of reaction time.     

Transesterification of soybean oil and analysis of bioproduct

Biodiesel produced by the transesterification reaction of soybean oil using potassium hydroxide (KOH) catalytic is a promising alternative fuel to diesel regarding the limited resources of fossil fuel and the environmental concerns. In order to decrease the operational temperature and increase the conversion efficiency of methanol, a novel idea was presented in which a co-solvent dichloromethane was added to the reactants. The results showed that the yield of methyl ester was improved when dichloromethane was coexistence. The effects of the co-solvent, molar ratio of methanol/oil, reaction temperature, and catalyst on the biodiesel conversion were investigated. With the optimal reaction temperature of 45 °C, methanol to oil ratio of 4.5:1, co-solvent dichloromethane of 4.0%, a 96% yield of methyl esters was observed in 2.0 h at the condition with 1.0 wt.% potassium hydroxide. The characterization and analysis of biodiesel were obtained by FT-IR, gas chromatograph and inductively coupled plasma atomic emission (ICP–OES) spectroscopy methods. The cetane number, flash point, cold filter plugging point, acid number, water content, ash content and total glycerol content were investigated.     

Enzymatic production of biodiesel from Pistacia chinensis bge seed oil using immobilized lipase

Biodiesel fuel from renewable non-edible woody plant oils has recently attracted more attention due to its environmental benefits and the reduced costs of raw materials. This study investigated the enzymatic transesterification of Pistacia chinensis bge seed oil (PCO) with methanol. The recombinant Rhizopus oryzae lipases (ROL) immobilized on macroporous resin and anion exchange resin, named as MI-ROL and AI-ROL, respectively, were used as biocatalysts. The transesterification reaction catalyzed by the immobilized lipase was investigated in a solvent-free system. The highest biodiesel yields of 92% and 94% were achieved under the optimum conditions (enzyme dosage 25 IU_AI-ROL/g PCO or 7 IU_MI-ROL/g PCO, methanol to oil molar ratio 5:1, water content 20% by weight of oil, temperature 37 °C, and reaction time 60 h). There was no obvious loss in the yield of biodiesel after being consecutively used for five cycles in the transesterification reactions using AI-ROL, while the yield of biodiesel remained above 60% after the MI-ROL was repeatedly used for four cycles.     

Transesterification of palm oil with methanol in a reactive distillation column

The higher feedstock and processing costs for biodiesel production can be reduced by applying reactive distillation (RD) in transesterification process. The effects of reboiler temperature, amount of KOH catalyst, methanol to oil molar ratio and residence time on the methyl ester purity were determined by using a simple laboratory-scale RD packed column. The results indicated that from the empty column, the system reached the steady state in 8 h. Too high reboiler temperature and the amount of catalyst introduce more soap from saponification in the process. The optimal operating condition is at a reboiler temperature 90 °C, a methanol to oil molar ratio of 4.5:1.0, KOH of 1 wt.% respect to oil and 5 min of residence time in the column. This condition requires the fresh feed methanol 25% lower than in the conventional process and produces 92.27% methyl ester purity. Therefore this RD column can be applied in small or medium biodiesel enterprise.     

An experimental investigation of biodiesel synthesis from waste canola oil using supercritical methanol

Synthesis of biodiesel from waste canola oil using supercritical methanol is investigated under relatively moderate reaction conditions (240–270 °C/10 MPa) with residence time of 15–45 min and methanol to oil weight ratio of 1:1, 1.5:1 or 2:1. The effects of reaction conditions on the biodiesel yield were studied using design of experiments (DOE). The results showed that reaction time, temperature, and their interaction were the most significant factors on the yield. The highest biodiesel yield of 102% was achieved at 270 °C, 10 MPa, and methanol/oil weight ratio of 2 for 45 min reaction time. The GC–MS analysis of the reaction products showed that the by-product, glycerol, further reacted with methanol, generating methyl ethers of glycerol. Further confirmation of this side reaction was obtained by reacting glycerol and methanol at 270 °C/10 MPa for 15, 30, and 45 min. The experimental results showed these reactions could positively affect the overall biodiesel yield by providing oxygenated compounds such as 3-methoxy-1,2-propanediol, dimethoxymethane, and 2,2-dimethoxypropane as well as methyl palmitate and methyl oleate.     

Optimization of fish-oil-based biodiesel synthesis

In this study, the optimum conditions (methanol/oil mole ratio, temperature, and so on) for producing biodiesel with fish oil (menhaden oil) were established. The length of the carbon chain of fish oil is frequently greater than that of general vegetable oils. Therefore, the use of fish-oil based biodiesel with larger cetane number may improve diesel engine performance and result in a reduction of pollutant emissions. The optimum conditions of the manufacture of biodiesel with menhaden oil were reaction time of 120 min, reaction temperature of 55 °C, methanol/fish oil molar ratio of 12, and alkaline catalyst content of 2.0 wt%. In the performance evaluation of the biodiesel produced, the acid value (0.20 mg KOH/g), kinematic viscosity (4.60 cSt at 40 °C), and higher heating value (42.1 MJ/k) biodiesel quality standards were suitable.     

Intensified production of biodiesel using a spinning disk reactor

This work achieves continuous transesterification of soybean oil and methanol in a spinning disk reactor. The effects of the methanol-to-oil molar ratio, catalyst type, catalyst concentration, reaction temperature, flow rate, and rotational speed were investigated. Optimal yield of 96.9% was obtained with a residence time of 2–3 s at a molar ratio of 6, potassium hydroxide concentration of 1.5 wt%, temperature of 60 °C, flow rate of 773 mL/min, and rotational speed of 2400 rpm. The production rate of 1.86 mol/min was high compared to that of other reactors for continuous transesterification process, indicating that a spinning disk reactor is a promising alternative method for continuous biodiesel production.     

Transesterification of soybean oil to biodiesel using SrO as a solid base catalyst

In this study, transesterification of soybean oil to biodiesel using SrO as a solid base catalyst was studied. The reaction mechanism was proposed and the separate effects of reaction temperature, molar ratio of methanol to oil, mass ratio of catalyst to oil and repeated experiments were investigated. The results showed that the yield of biodiesel produced with SrO as a catalyst was in excess of 95% at temperatures below 70 °C within 30 min. SrO had a long catalyst lifetime and could maintain sustained activity even after being repeatedly used for 10 cycles. The results proved that transesterification of soybean oil to biodiesel using SrO as a catalyst is a commercially viable way to decrease the costs of biodiesel production.     

Macauba oil as an alternative feedstock for biodiesel: Characterization and ester conversion by the supercritical method

In this work different samples of Brazilian macauba oil obtained from mechanical pressing were characterized and production of esters of fatty acids using a catalyst-free continuous process under supercritical alcohols was assessed. Analysis of oil samples showed that the major fatty acid on pulp oil was oleic acid (mean value 62.8%), the amount of free fatty acid (FFA) was very high (37.4–65.4%), samples contained glycerides (7.4–16.5% TAG, 14.2–16.8% DAG and 1.0–3.4% MAG) and moisture was around 1.0%. Oil was processed in a continuous reactor using supercritical methanol or ethanol and the effects of temperature (573, 598, 623 and 648 K), pressure (10, 15 and 20 MPa), oil to alcohol molar ratio (1:20, 1:30 and 1:40), water concentration (0, 5 and 10 wt% added) and the flow rate of reaction mixture (1.0, 1.5, 2.0, 2.5 and 3.0 mL/min) on process efficiency were evaluated. The highest ester content achieved in reactions with supercritical methanol was 78.5% (648 K, 15 MPa, 1:30 oil:methanol molar ratio, 5 wt% water and 2.5 mL/min flow rate), while with supercritical ethanol was 69.6% (598 K, 15 MPa, 1:30 oil:ethanol molar ratio, 5 wt% water and 2.0 mL/min flow rate). The extent of the reaction was explored using a novel parameter, convertibility, which corresponds to the maximum ester content attainable from the feedstock. According to the convertibility of macauba pulp oil, the highest ester content corresponded to efficiencies of 98.0% and 86.9%, respectively. Results demonstrate that macauba oil might be a potential alternative for biodiesel production, though purification steps should be taken into account to achieve biodiesel specifications.     

Optimization of Process Variables for Biodiesel Production Using the Nanomagnetic Catalyst CaO/NaY‐Fe3O4

Due to decreasing oil resources, alternative fuels such as biodiesel are required. The nanomagnetic catalyst CaO/NaY‐Fe₃O₄ was synthesized and used for biodiesel production from canola oil. The structure of the catalysts was characterized by X‐ray diffraction, field emission scanning electron microscopy, Brunauer‐Emmett‐Teller method, Fourier transform infrared spectroscopy, and vibrating sample magnetometer method. To optimize the influence of the operating variables, such as the methanol/canola oil molar ratio, the amount of catalyst, and the reaction time, on the yield of transesterification reaction, an experimental design was applied based on the Box‐Behnken method. The optimum values of these variables were predicted by the cubic model and were in excellent agreement with the experimental results.     

Biodiesel production from highly unsaturated feedstock via simultaneous transesterification and partial hydrogenation in supercritical methanol

In this study, a supercritical one-pot process combining transesterification and partial hydrogenation was proposed to test its technical feasibility. Simultaneous transesterification of soybean oil and partial hydrogenation of polyunsaturated compounds over Cu catalyst in supercritical methanol was performed at 320 °C and 20 MPa. Hydrogenation proceeded simultaneously during the transesterification of soybean oil in supercritical methanol, and hydrogenation occurred during the reaction despite the absence of hydrogen gas. The polyunsaturated methyl esters obtained in the biodiesel were mainly converted to monounsaturated methyl esters by partial hydrogenation. Key properties of the partially hydrogenated methyl esters were improved and complied with standard specifications for biodiesel.     

工业硫酸催化酯化合成生物柴油性能的研究

以各种植物油厂的下脚油、高脂肪酸厂的废弃产物和甲醇为原料,以工业硫酸为催化剂,催化合成生物柴油。考察了醇油体积比、催化剂用量、反应时间以及温度对酯化率的影响,确定了最佳反应条件:醇油体积比1∶1,催化剂用量0.6g,反应温度65～75℃,反应时间6h。在此条件下,酯化率达到95.5%。将产物进行常压蒸馏、水洗,得到柴油粗产品。再将柴油粗产品在-0.095～-0.085MPa真空度下减压蒸馏精制,收集170～210℃范围内的馏分。其精制所得产品酸值低,且收率高达90%以上。制得的生物柴油的基本性质如密度、黏度、闪点等基本符合美国现有的生物柴油标准,且与石化矿物柴油性质接近。     

Biodiesel production from Croton megalocarpus oil and its process optimization

Production of biodiesel from non-edible feedstocks is attracting more attention than in the past, for the purpose of manufacturing alternative fuels without interfering with the food chain. Biodiesel was produced using Croton megalocarpus oil as a non-edible feedstock. C. megalocarpus oil was obtained from north Tanzania. This study aimed at optimizing the biodiesel production process parameters experimentally. The parameters involved in the optimization process were the amount of the catalyst, of alcohol, temperature, agitation speed and reaction time. The optimum biodiesel conversion efficiency obtained was 88% at the optimal conditions of 1.0 wt.% amount of potassium hydroxide catalyst, 30 wt.% amount of methanol, 60 °C reaction temperature, 400 rpm agitation rate and 60 min reaction time. The properties of croton biodiesel which were determined fell within the recommended biodiesel standards. Croton oil was found with a free fatty acid content of 1.68% which is below the 2% recommended for the application of the one step alkaline transesterification method. The most remarkable feature of croton biodiesel is its cold flow properties. This biodiesel yielded a cloud and pour point of −4 °C and −9 °C, respectively, while its kinematic viscosity lay within the recommended standard value. This points to the viability of using croton biodiesel in cold regions.     

KOH/bentonite catalysts for transesterification of palm oil to biodiesel

A potential application of KOH/bentonite as a catalyst for biodiesel production was studied. A series of KOH/bentonite catalysts was prepared by impregnation of bentonite from Pacitan with potassium hydroxide. The ratios between KOH and bentonite were 1:20, 1:10, 1:5, 1:4, 1:3, and 1:2. The characterization of KOH/bentonite and natural bentonite was conducted by nitrogen adsorption and XRD analysis. The effects of various reaction variables on the yield of biodiesel were investigated. The highest yield of biodiesel over KOH/bentonite catalyst was 90.70 ± 2.47%. It was obtained at KOH/bentonite 1:4, reaction time of 3 h, 3% catalyst, methanol to oil ratio of 6, and the reaction temperature at 60 °C.     

Biodiesel synthesis from waste vegetable oil via transesterification reaction in supercritical methanol

Response surface methodology (RSM) was applied to analyze the effect of four independent variables (molar ratio of methanol to oil, reaction temperature, pressure and time) on the yield of the biodiesel production via supercritical methanol (SCM) method. Waste vegetable oil (WVO) was used as raw material and transesterification reaction was performed in a supercritical batch reactor. The central composite rotatable design was used to maximize the yield of the biodiesel. The optimal values of variables were determined by RSM to be 33.8:1 (methanol/oil molar ratio) 271.1 °C, 23.1 MPa and 20.4 min reaction time for the maximum predicted yield of 95.27% (g/g). Moreover, an irreversible first order kinetic model was successfully correlated to the experimental transesterification data with 3.37 (s⁻¹) and 31.71 (kJ/mol) as the frequency factor and activation energy of the process.     

NaOH/PAM催化剂对合成生物柴油的影响

大麻籽油和甲醇经NaOH/PAM催化合成生物柴油,本实验在醇油比固定的情况下考察了催化剂的碱含量、催化剂用量对酯交换转化率的影响、碱量及反应时间分别对转化率和皂化百分数的影响,采用红外光谱技术对催化剂进行分析,确定了较适宜的反应条件.结果表明:实际碱量随NaOH添加量的增加而增加；催化剂用量增加,原料油转化率增加；反应时间的增加,原料油转化率曲线增加到一定水平后趋于平缓；较适宜的反应条件为PN-4催化剂用量3％,反应时间为60 min.     

Continuous production of biodiesel from cottonseed oil and methanol using a column reactor packed with calcined sodium silicate base catalyst☆

Sodium silicate and that calcined at 400 °C for 2 h were used to catalyze the transesterification of cottonseed oil with methanol. Calcined sodium silicate(CSS) catalyst exhibited much higher catalytic activity and stability. A maximum biodiesel yield of 98.9% was achieved at methanol/oil mole ratio of 12:1, reaction temperature65 °C, reaction time 3.0 h, and CSS/oil mass ratio of 2 wt%. After 7 consecutive reactions without any treatment,biodiesel yield reduced to 82.5%. Considering technological and economic feasibility, CSS base catalyst supported on θ rings was prepared for continuous transesterification. The maximum yield was 99.1% under optimum conditions(reaction temperature 55 °C, methanol velocity 1 ml·min-1, oil velocity 3 ml·min-1, and 5 tower sections). These results indicate that this new continuous biodiesel production process and apparatus present a great potential for industrial application in biodiesel.     

Basic ionic liquid immobilized oxides as heterogeneous catalyst for biodiesel synthesis from waste cooking oil

The basic ionic liquid (IL) [Bmin]OH was synthesized and immobilized onto oxide surface to obtain IL/Mg-Al and IL/Mg-Al-La catalysts. The catalysts were characterized by FT-IR, XRD, EDS, BET and basic test. The results proved that the IL immobilized oxides exhibited high activity for biodiesel synthesis from waste cooking oil. The high FAME yield of 98.7% could be obtained at 338 K, 12:1 methanol to oil, 3 wt% catalyst amount and 6 h reaction time by IL/Mg-Al-La catalysts.