茶油精炼副产物皂脚制备生物柴油的研究

以茶油精炼副产物皂脚和甲醇为原料,NaOH为催化剂,经酯交换合成生物柴油,研究了工艺条件对皂脚合成生物柴油收率的影响。结果表明,适宜的工艺条件为:醇油摩尔比为5∶1,反应时间为30 min,反应温度为30℃,催化剂NaOH用量为油重的0.7%,反应收率为98.0%。     

叔丁醇共溶剂用于制备生物柴油的研究

利用叔丁醇作为共溶剂可使棕榈油、甲醇和催化剂形成均相体系,用于酯交换反应制备生物柴油,可以缩短反应时间。实验以棕榈油为原料,氢氧化钠为催化剂,在带夹套的玻璃反应器内进行反应。考察了共溶剂质量分数、催化剂质量分数、反应温度、醇油摩尔比等因素对生物柴油产率的影响,获得了最佳反应条件。实验结果表明,当叔丁醇质量为棕榈油质量的11.6%,催化剂质量为油质量的1.0%,反应温度为60℃,醇油摩尔比为6∶1时,反应2 m in后生物柴油产率达到了90%。     

微波强化棉籽油制备生物柴油的研究

利用微波强化以棉籽油和甲醇为原料,KOH为催化剂制备生物柴油。考察醇油摩尔比、催化剂用量、反应时间和微波功率对酯交换反应的影响。结果表明,醇油摩尔比为9∶1,催化剂用量为1.0%,反应时间为3 min,微波功率360 W为最优反应条件。在此反应条件下生物柴油产率可达94%。与传统合成方法相比,该方法可缩短反应时间30~35 min。所得生物柴油主要质量指标达到我国和欧洲(EN14214)生物柴油质量标准,通过红外光谱分析表明,棉籽油生物柴油具有生物柴油所含的官能团。     

Production of mixed methyl/ethyl esters from waste fish oil through transesterification with mixed methanol/ethanol system

Biodiesel (mixed fatty acid methyl/ethyl esters) was prepared from waste fish oil through base-catalyzed transesterification with mixed methanol/ethanol system. Effect of methanol/ethanol (% v/v), type and concentration of the catalyst, mixed alcohols to oil molar ratio, the reaction temperature, and the reaction time on the biodiesel yield was optimized. Maximum biodiesel yield (97.30?wt%) was produced by implementing 1:1 methanol/ethanol (v/v), 1.0?wt% KOH, 6:1 mixed alcohols to oil molar ratio, 40°C reaction temperature, and 30?min of reaction time. Conversion of the waste fish oil to mixed methyl/ethyl esters was confirmed by ¹H NMR spectroscopy. Fuel properties of the resulting biodiesel in addition to its blends with petrodiesel were in good agreement with specifications of ASTM D6751 and ASTM D7467, respectively. Therefore, it was concluded that using mixed alcohol system for biodiesel production could reduce the production cost through reducing conditions required for maximum conversion.     

Conversion of waste cooking oil to biodiesel using ferric sulfate and supercritical methanol processes

In this comparative study, conversion of waste cooking oil to methyl esters was carried out using the ferric sulfate and the supercritical methanol processes. A two-step transesterification process was used to remove the high free fatty acid contents in the waste cooking oil (WCO). This process resulted in a feedstock to biodiesel conversion yield of about 85-96% using a ferric sulfate catalyst. In the supercritical methanol transesterification method, the yield of biodiesel was about 50-65% in only 15 min of reaction time. The test results revealed that supercritical process method is probably a promising alternative method to the traditional two-step transesterification process using a ferric sulfate catalyst for waste cooking oil conversion. The important variables affecting the methyl ester yield during the transesterification reaction are the molar ratio of alcohol to oil, the catalyst amount and the reaction temperature. The analysis of oil properties, fuel properties and process parameter optimization for the waste cooking oil conversion are also presented.     

Biodiesel production from soybean oil using modified calcium loaded on rice husk activated carbon as a low-cost basic catalyst

Activated carbon was obtained by hydrothermal process using rice husk as raw materials. The study in our lab had been developed to produce high-quality biodiesel from soybean oil with the activated carbon-base catalyst. The polyethylene glycol (PEG 400) modified calcium loaded on the rice husk activated carbon (CaO/AC) catalyst was prepared via the dipping method and then was used as a heterogeneous solid-base catalyst to produce biodiesel. The effects of CaO/AC ratio and calcination time on catalytic performance were researched according to the yield of biodiesel, and the optimum reaction conditions for biodiesel from soybean oil via PEG 400–modified CaO/AC catalyst were evaluated. The results showed that the yield of fatty acid methyl ester (FAME) achieved 93.01% at the reaction temperature of 342 K, methanol/oil molar ratio of 10:1, and reaction time of 6 h. All in all, modified CaO/AC catalyst showed very high activity for transesterification of soybean oil and had catalytic repeated availability.     

Parametric study of biodiesel production from used soybean oil

Biodiesel, an alternative diesel fuel derived from vegetable oil, animal fat, or waste vegetable oil (WVO), is obtained by reacting the oil or fat with an alcohol (transesterification) in the presence of a basic catalyst to produce the corresponding mono‐alkyl esters. In this work, the effect of the catalyst KOH‐to‐WVO ratio, ethanol concentration, and time of reaction on the biodiesel yield were investigated. The transesterification reaction was performed at a constant temperature (35 °C) in order to minimize the cost of heating and ethanol evaporation. A 2³ complete factorial design on biodiesel yield (Y) was performed using low and high levels of operating variables: KOH concentration (9–14 g/L), ethanol concentration (30–40 vol‐%) and time (30–40 min). The complete factorial model that can be used to fit the data was determined. The model shows that interactions exist among the parameters and that the parameters, or factors, do not operate independently on the response (biodiesel yield). The highest yield was obtained in the first 30 min of reaction time. The results indicate that the highest yield was 78.5 vol‐% using a KOH‐to‐WVO ratio of 12 g/L and 30 vol‐% ethanol. The ASTM tests indicate that the biodiesel properties are within the biodiesel standard limits.     

Synthesis and characterization of mono‐acylglycerols through the glycerolysis of methyl esters obtained from linseed oil

Here we investigate the production and characterization of mono‐acylglycerols through the glycerolysis of biodiesel, a methyl ester mixture, obtained from linseed oil. The biodiesel employed was derived from linseed oil through transesterification according to transesterification double step process 1 . The efficiency of H₂SO₄, CaO, and NaOH as catalysts was evaluated for the production of mono‐acylglycerols. The glycerolysis reactions were performed by varying the molar ratio of the reagents (biodiesel:glycerol), the type and amount of catalyst, reaction time and temperature. Systematic evaluation of reaction yield is shown as a function of these parameters. Reaction products were characterized through IR spectroscopy, hydrogen NMR, and the GC techniques. The study of three different catalysts indicated that the most efficient was 5% NaOH in a 1:5 biodiesel–glycerol molar ratio with 10 h reaction time. The reaction reached a maximum of 85% biodiesel conversion with a mono‐acylglycerol yield of 72% at 130°C.     

大豆油异丙酯的合成研究

用碱催化酯交换法合成大豆油异丙酯,考察了醇油摩尔比、催化剂用量、反应温度、反应时间对酯交换反应的影响。结果表明,合成大豆油异丙酯的最佳条件如下:醇油摩尔比10∶1,反应时间60 min,反应温度80℃,碱催化剂浓度2.0%。在此条件下,大豆油异丙酯的产率达53.07%。最后对比研究了大豆油甲酯、乙酯、异丙酯的合成,得出不同结构的醇与大豆油进行酯交换反应的规律。色谱表征表明,经酯交换作用,原料油成功转化为生物柴油。     

棉籽油酯交换法合成生物柴油的工艺研究

介绍了利用复合碱性催化棉籽油酯交换合成生物柴油的工艺过程,正交实验得出的适宜工艺条件为:醇油摩尔比为5.5∶1,反应时间50 min,反应温度35℃,催化剂用量1.0%,产率可达96%。并比较了生物柴油与0#柴油的性能。     

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.     

Metakaolinite as a catalyst for biodiesel production from waste cooking oil

The use of metakaolinite as a catalyst in the transesterification reaction of waste cooking oil with methanol to obtain fatty acid methyl esters (biodiesel) was studied. Kaolinite was thermally activated by dehydroxylation to obtain the metakaolinite phase. Metakaolinite samples were characterized using X-ray diffraction, N₂ adsorption-desorption, simultaneous thermo-gravimetric analyse/differential scanning calorimetry (TGA/DSC) experiments on the thermal decomposition of kaolinite and Fourier-transform infrared spectrometer (FTIR) analysis. Parameters related to the transesterification reaction, including temperature, time, the amount of catalyst and the molar ratio of waste cooking oil to methanol, were also investigated. The transesterification reaction produced biodiesel in a maximum yield of 95% under the following conditions: metakaolinite, 5 wt-% (relative to oil); molar ratio of oil to methanol, 1∶23; reaction temperature, 160°C; reaction time, 4 h. After eight consecutive reaction cycles, the metakaolinite can be recovered and reused after being washed and dried. The biodiesel thus obtained exhibited a viscosity of 5.4?mm²?s^–1 and a density of 900.1 kg?m^–3. The results showed that metakaolinite is a prominent, inexpensive, reusable and thermally stable catalyst for the transesterification of waste cooking oil.     

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.     

Synthesis and characterization of poppy seed oil methyl esters

Response surface methodology(RSM) was used to determine the optimum conditions of the methanolysis of crude poppy seed oil using Na OCH3 as catalyst. The experiments were run according to five levels, four variable central composite rotatable design(CCRD) using RSM. The reaction variables, i.e., molar ratio of methanol/oil(3:1–9:1), catalyst concentration(0.5 wt%–1.25 wt% Na OCH3), reaction temperature(25–65 °C), and reaction time(20–90 min) were studied. We demonstrated that the molar ratio of methanol/oil, catalyst concentration,and reaction temperature were the significant parameters affecting the yield of poppy seed oil methyl esters(PSOMEs). The optimum transesterification reaction conditions, established using the RSM, which offered a89.35% PSOME yield, were found to be 7.5:1 molar ratio of methanol/oil, 0.75% catalyst concentration, 45 °C reaction temperature, and 90 min reaction time. The proposed process provided an average biodiesel yield of more than 85%. A linear correlation was constructed between the observed and predicted values of the yield.The gas chromatography(GC) analyses have shown that PSOMEs contain linoleic-, oleic-, palmitic-, and stearic-acids as main fatty acids. The FTIR spectrum of the PSOMEs was also analyzed to confirm the completion of the transesterification reaction. The fuel properties of the PSOMEs were discussed in light of biodiesel standards(ASTM D 6751 and EN 14214).     

Feasibility of Palm Oil as the Feedstock for Biodiesel Production via Heterogeneous Transesterification

The production of biodiesel has become popular recently as a result of increasing demand for a clean, safe and renewable energy. Biodiesel is made from natural renewable sources such as vegetable oils and animal fats. The conventional method of producing biodiesel is by reacting vegetable oil with alcohol in the presence of a homogenous catalyst (NaOH). However, this conventional method has some limitations such as the formation of soap, usage of significant quantities of wash water and complicated separation processes. Heterogeneous processes using solid catalysts have significant advantages over homogenous methods. Currently, more than 90 % of world biodiesel is produced using rapeseed oil. The production of biodiesel from rapeseed oil is considered uneconomical, considering the fact that palm oil is currently the world's cheapest vegetable oil. Therefore, the focus of this study is to show the feasibility of producing biodiesel from palm oil using montmorillonite KSF as a heterogeneous catalyst. The heterogeneous transesterification process was studied using design of experiment (DOE), specifically response surface methodology (RSM) based on a four‐variable central composite design (CCD) with α = 2. The transesterification process variables were reaction temperature, x₁ (50–190 °C), reaction period, x₂ (60–300 min), methanol/oil ratio, x₃ (4–12 mol mol^–1) and the amount of catalyst, x₄ (1–5 wt %). It was found that the conversion of palm oil to biodiesel can reach up to 78.7 % using the following reaction conditions: reaction temperature of 155 °C, reaction period of 120 min, ratio of methanol/oil at 10:1 mol mol^–1 and amount of catalyst at 4 wt %. From this study, it was shown that montmorillonite KSF catalyst can be used as a solid catalyst for biodiesel production from palm oil.     

Influence of the glycerin content in the preparation of calcium diglyceroxide from eggshell applied in the residual oil transesterification

Currently, biodiesel is pointed out worldwide as the main alternative in the complementation and substitution of petrochemical diesel. However, the current industrial route of synthesis of this biofuel depends on the cost of raw materials (which are also destined for food purposes) and the expense of the production process. Aiming to remedy this obstacle, the use of solid, sustainable, low-cost, efficient, and reusable catalysts in residual raw materials, such as waste cooking oils, has been highlighted as a promising alternative. This work focused on studying the influence of the glycerin content used in the preparation by wet impregnation of catalyst calcium diglyceroxide in the efficiency of transesterification of waste cooking oil. The catalyst was synthesized from CaO from chicken eggshell, raw glycerin co-product from biodiesel, and methanol. The transesterification reactions were performed using 120 g of frying residual oil, methanol: oil molar rate of 6:1, constant shaking, and reaction temperature of 63 ± 1°C for 180 min. The catalyst material synthesized with residual glycerin was active for four reactions (without reactivation of its sites) with high percentages of efficiency of 96.13, 96.85, 95.93, and 91.65, respectively. It was noted that the glycerol purity correlated with changes in the structural morphology of the final compound, as well as changes in the leaching rate, acidity index, water content, and ester content of the blends. It was found that adding 15% water to the lipid material correlated with an increase in ester content (99%) in the synthesized biodiesel.     

气升式反应器二步法生产生物柴油实验研究

以酸化油为原料,利用气升式反应器二步法生产生物柴油.通过实验优化出预酯化反应和酯交换反应的最佳工艺条件和气升式反应装置的最佳工艺参数.气升式反应器的最佳工艺操作参数为:预酯化反应,反应温度115℃,反应时间2 h,催化剂质量分数1%,甲醇通入速度6.5 L/h;酯交换反应,反应温度70℃,反应时间1 h,催化剂质量分数...     

微碱强化超临界法制备生物柴油组分分析及工艺过程

对超临界条件下添加微量氢氧化钾催化碳酸二甲酯与棕榈油制备无甘油副产的生物柴油反应进行了研究,微碱的添加有效降低了苛刻的反应条件。利用气质联用技术对反应产物的组分进行了定性确证并建立了产物的定量分析方法。结果表明,酯交换反应的产物组分为甘油碳酸酯、脂肪酸甲酯、甘油单酯、脂肪酸甘油碳酸酯、甘油二酯和甘油三酯。考察了反应温度、反应时间、酯油摩尔比以及催化剂添加量对酯交换反应的影响。当反应温度280℃、反应时间20 min、KOH添加量为0.1%、酯油摩尔比20:1、反应压力3.5MPa时,脂肪酸甲酯的收率可达到83.11%。     

Supercritical transesterification: Impact of different types of alcohol on biodiesel yield and LCA results

A series of experiments with transesterification of rapeseed oil in supercritical methanol and supercritical ethanol was carried out in a batch reactor at various reaction temperatures (250–350 °C), working pressure (8–12 MPa), reaction time (7, 15 and 30 min), and at a constant 42:1 alcohol to oil molar ratio. The effect of alcohol, temperature, pressure and reaction time on biodiesel yield was investigated using linear multiple regression models. In the observed range, temperature has the highest impact on yields, followed by reaction time and pressure. The relative importance of time and pressure in explaining yields is higher in the case of transesterification in supercritical ethanol. The results of environmental life cycle assessment have revealed that contrary to general belief the usage of ethanol instead of methanol cannot improve the sustainability and renewability of the transesterification process significantly.     

Biodiesel production from oleander (<Emphasis Type="Italic">Thevetia Peruviana</Emphasis>) oil and its performance testing on a diesel engine

Oleander oil has been used as raw material for producing biodiesel using ultrasonic irradiation method at the frequency of 20 kHz and horn type reactor 50 watt. A two-step transesterification process was carried out for optimum condition of 0.45 v/v methanol to oil ratio, 1.2% v/v H₂SO₄ catalyst, 45 °C reaction temperature and 15min reaction time, followed by treatment with 0.25 v/v methanol to oil ratio, 0.75% w/v KOH alkaline catalyst, 50 °C reaction temperature and 15 min reaction time. The fuel properties of Oleander biodiesel so obtained confirmed the requirements of both the standards ASTM D6751 and EN 14214 for biodiesel. Further Oleander biodiesel-diesel blends were tested to evaluate the engine performance and emission characteristics. The performance and emission of 20% Oleander biodiesel blend (B20) gave a satisfactory result in diesel engines as the brake thermal efficiency increased 2.06% and CO and UHC emissions decreased 41.4% and 32.3% respectively, compared to mineral diesel. Comparative investigation of performance and emissions characteristics of Oleander biodiesel blends and mineral diesel showed that oleander seed is a potential source of biodiesel and blends up to 20% can be used for realizing better performance from an unmodified diesel engine.