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 using tetramethyl- and benzyltrimethyl ammonium hydroxides as strong base catalysts

In recent years, the acceptance of fatty acid methyl esters (biodiesel) as an alternative fuel has rapidly grown in EU. The most common method for biodiesel production is based on triglyceride transesterification to methyl esters with dissolved sodium hydroxide in methanol as catalyst. In this study, cottonseed oil and used frying oil were subjected to the transesterification reaction with tetramethyl ammonium hydroxide and benzyltrimethyl ammonium hydroxide as strong base catalysts. This work investigates the optimum conditions for biodiesel production using amine-based liquid catalysts. Biodiesel ester content was strongly related with the type of feedstock and the reaction variables, such as those of the catalyst concentration, methanol to oil molar ratio, and reaction time. The overall results suggested that the transesterification of cottonseed oil achieved high conversion rates with both catalysts, while the use of waste oil resulted in lower yields of methyl esters due to the possible formation of amides.     

酸性离子液体［(CH2)4SO3HMIM］［HSO4］催化潲水油制备生物柴油的研究

制备了酸性离子液体[(CH₂)₄SO₃HMIM］［HSO₄］并用于催化潲水油制备生物柴油,研究了反应时间、反应温度、醇油物质的量比和剂油物质的量比等对酯交换反应转化率的影响,确定了较适宜的反应条件。结果表明,在反应时间4 h、反应温度140 ℃、醇油物质的量比12和剂油物质的量比0.08条件下,酯交换反应转化率为92.13%。制备的生物柴油达到了中国柴油机燃料调合用生物柴油(BD100)标准GB/T20828-2007。     

Life cycle analysis of biodiesel production

Biodiesel has attracted considerable attention as a renewable, biodegradable, and nontoxic fuel and can contribute to solving the energy problems, significantly reducing the emission of gases which cause global warming.The first stage of this work was to simulate different alternative processes for producing biodiesel. The method used for the production of biodiesel is the transesterification of vegetable oils with an alcohol in the presence of a catalyst. The raw materials used were palm oils and waste cooking oil.The second stage was a life cycle analysis for all alternatives under study, followed by an economic analysis for the alternatives that present minor impacts and which are more promising from an economic point of view. Finally, we proceeded to compare the different alternatives from both the point of view of life cycle and economic analysis.The feasibility of all processes was proven and the biodiesel obtained had good specifications.From the standpoint of life cycle analysis, the best alternative was the process of alkaline catalysis with acid pre-treatment for waste cooking oil.The economic analysis was done to the previous mentioned process and to the process that uses raw virgin oils, methanol, and sodium hydroxide. This process has lower investment costs but the process of alkaline catalysis with acid pre-treatment, whose main raw material is waste oil, is much more profitable and has less environmental impacts.     

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.     

棉籽油二乙二醇甲醚酯新型生物柴油制备

以精制棉籽油、无水甲醇和二乙二醇单甲醚为原料,KOH为催化剂,通过酯交换反应制备出一种高含氧量的新型生物柴油;采用正交试验研究了醇油比、催化剂用量、温度和反应时间对产率的影响,得出了最佳合成条件;运用红外光谱法、核磁共振法、凝胶渗透色谱法进行了产物结构表征;此外柴油机台架试验也表明燃烧该新型生物柴油可有效减少柴油机的废气排放。     

利用废豆油制备生物柴油

研究了利用废豆油和甲醇作为原料,在催化剂甲醇钠的作用下通过酯交换反应,制备脂肪酸甲酯即生物柴油和丙三醇(甘油),根据正交实验结果,较佳的工艺条件为:摩尔比7∶1、反应温度60℃、反应时间90min、催化剂用量0.8%。在此工艺条件下,生物柴油的收率可达93.71%;精馏后的甘油纯度较高,达到97.5%以上。     

Optimization of transesterification for methyl ester production from chicken fat

In this study, low cost feedstock chicken fat was used to produce methyl ester. After reducing the free fatty acid level of the chicken fat less than 1%, the transesterification reaction was completed with alkaline catalyst. Potassium hydroxide, sodium hydroxide, potassium methoxide and sodium methoxide were used as catalyst and methanol was used as alcohol for transesterification reactions. The effects of catalyst type, reaction temperature and reaction time on the fuel properties of methyl esters were investigated. The produced chicken fat methyl esters were characterized by determining their viscosity, density, pour point, flash point, acid value, methanol content, heat of combustion value, total-free glycerin, mono-di-tri glycerides, copper strip corrosion and ester yield values. The measured fuel properties of the chicken fat methyl ester met EN 14214 and ASTM D6751 biodiesel specifications when using potassium hydroxide and sodium hydroxide catalysts with high ester yield.     

Biodiesel production from waste animal fats using pyrolysis method

It is necessary to utilize waste cooking oil as a raw material of biodiesel because the land area available for cultivation in Japan is limited. Waste cooking oil also includes long-chain saturated compounds and free fatty acids derived from animal fats. The former has a high freezing point and the latter forms a soap with the alkali catalyst typically used in biodiesel production, reducing the yield. To make waste cooking oil available for biodiesel production, pyrolysis of the waste oil was attempted. The resulting triacylglycerols were found to decompose at 360 to 390 °C, fatty acids were generated by cleavage of the ester bond, and short-chain hydrocarbons and short-chain fatty acids were generated by cleavage of the unsaturated bonds in the hydrocarbon chain. When the retention time was extended with a reaction temperature of 420 °C, light-oil hydrocarbons were generated by decarboxylation of the fatty acids. By adding palladium supported by activated carbon (Pd/C) as a catalyst, decarboxylation was promoted, and hydrocarbons comparable to light oil were selectively obtained in high yield at 85 wt.%. Compared to the biodiesel obtained by transesterification, the biodiesel obtained by pyrolysis showed improvement of about − 5 °C in the pseudo-cold filter plugging point.     

Na/SiO2新型固体碱催化制备生物柴油的研究

以NaOH、正硅酸乙酯和乙醇为原料,经溶胶-凝胶法制备新型固体碱催化剂（Na/SiO₂）,用于催化大豆油与甲醇的酯交换反应制备生物柴油,研究催化剂焙烧温度、n(NaOH)∶n(SiO₂)、n(甲醇)∶n(大豆油)、催化剂用量和反应时间对产率的影响以及催化剂的稳定性。结果表明,固体碱催化剂Na/SiO₂在大豆油与甲醇的酯交换反应中具有较高的催化活性,在催化剂焙烧温度600 ℃、n(NaOH)∶n(SiO₂)=2∶1、n(甲醇)∶n(大豆油)=15∶1、催化剂用量为大豆油质量的7%和反应时间3 h的条件下,脂肪酸甲酯产率可达97.42%,催化剂在稳定性试验中呈现出优良的稳定性。     

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%。     

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。     

Beef tallow biodiesel produced in a pilot scale

In the present work, the process of biodiesel production in a pilot plant has been studied using beef tallow as raw materials with methanol and potassium hydroxide as catalyst. The biodiesel quality is regulated by Brazilian specifications (Resolution 42) by the National Agency of Petroleum (ANP). The alkaline transesterification of animal fat with methanol produces a biodiesel with high quality and also with a good conversion rate. The process is possible but the economical viability must be improved by recovering methanol and glycerin. The obtained results have been used for industrial scale up of the process.     

Biodiesel production from high FFA rubber seed oil

Currently, most of the biodiesel is produced from the refined/edible type oils using methanol and an alkaline catalyst. However, large amount of non-edible type oils and fats are available. The difficulty with alkaline-esterification of these oils is that they often contain large amounts of free fatty acids (FFA). These free fatty acids quickly react with the alkaline catalyst to produce soaps that inhibit the separation of the ester and glycerin. A two-step transesterification process is developed to convert the high FFA oils to its mono-esters. The first step, acid catalyzed esterification reduces the FFA content of the oil to less than 2%. The second step, alkaline catalyzed transesterification process converts the products of the first step to its mono-esters and glycerol. The major factors affect the conversion efficiency of the process such as molar ratio, amount of catalyst, reaction temperature and reaction duration is analyzed. The two-step esterification procedure converts rubber seed oil to its methyl esters. The viscosity of biodiesel oil is nearer to that of diesel and the calorific value is about 14% less than that of diesel. The important properties of biodiesel such as specific gravity, flash point, cloud point and pour point are found out and compared with that of diesel. This study supports the production of biodiesel from unrefined rubber seed oil as a viable alternative to the diesel fuel.     

Use of dolomite catalyst in biodiesel production via transesterification of waste cooking oil in oscillatory baffled reactor

Biodiesel has recently gained popularity due to its environmental issues and the fact that it is generated from renewable resources. However, the cost of the synthesis of biodiesel is the major impediment to commercialization. The utilization of leftover cooking oils as raw material, the adaptation of a continuous transesterification process, and the use of cheap catalysts are the major possibilities for investigating the cost of biodiesel. In this work, a dolomite catalyst was prepared from natural dolomite rocks and used for the evaluation of continuous transesterification of biodiesel from oleic acid as a model compound of waste cooking oil (WCO). The dolomite catalyst was prepared by activation under vacuum at a surface area of 34.5 m²/g. The characterization tests showed good thermal stability of the catalyst and evolution of the CaO and MgO compounds at high concentrations. A kinetic study was conducted to obtain kinetic parameters of catalytic transesterification of the WCO. The kinetic experiments were carried out at 298–333 K, and residence time up to 80 min. The results presented that the catalytic transesterification is the first-order reaction, and the activation energy was 43 kJ/mol. The oscillatory baffled reactor (OBR) was used to evaluate the dolomite catalyst for the continuous production of biodiesel via transesterification. The evaluation study was conducted at a methanol: oil mole ratio of 6:1 and the effect of different operation variables on oleic acid conversion to biodiesel was studied. These variables were temperature (323, 333, and 343 K), residence times (5–40 min), the amplitude of oscillation (2–8 mm), and frequency of oscillation (1, 2, 3, 4, and 4.3 Hz). The results showed an outstanding performance and stable activity of the dolomite catalyst as a conversion of 96% was obtained at 333 K, 4.3 Hz, 8 mm amplitude, and 40 min residence time.     

Transesterification of neat and used frying oil: Optimization for biodiesel production

In this study, the characteristics and performance of three commonly used catalysts used for alkaline-catalyzed transesterification i.e. sodium hydroxide, potassium hydroxide and sodium methoxide, were evaluated using edible Canola oil and used frying oil. The fuel properties of biodiesel produced from these catalysts, such as ester content, kinematic viscosity and acid value, were measured and compared. With intermediate catalytic activity and a much lower cost sodium hydroxide was found to be more superior than the other two catalysts. The process variables that influence the transesterification of triglycerides, such as catalyst concentration, molar ratio of methanol to raw oil, reaction time, reaction temperature, and free fatty acids content of raw oil in the reaction system, were investigated and optimized. This paper also studied the influence of the physical and chemical properties of the feedstock oils on the alkaline-catalyzed transesterification process and determined the optimal transesterification reaction conditions that produce the maximum ester content and yield.     

甲醇钠催化地沟油制备生物柴油研究

以浓硫酸为催化剂,高酸值地沟油与甲醇酯化反应降酸的最优工艺条件为:n(甲醇):n(地沟油)=9:1,m(浓硫酸):m(地沟油)=1.1％,反应温度60℃,反应时间5h.制备生物柴油的最优工艺条件为:以甲醇钠为催化剂,反应时间2h,反应温度65℃,n(甲醇):n(地沟油)=7:1,m(甲醇钠):m(地沟油)=0.8％.制...     

Transesterification of rapeseed oil in subcritical methanol conditions

In this study, transesterification of rapeseed oil using subcritical methanol conditions was studied. The objective of the work was characterizing the methyl esters for its use as biodiesel in compression ignition motors. The variables affecting the methyl ester yield during the transesterification reaction, such as, the catalyst type and content, reaction temperature and pressure, the presence of hexane as co-solvent, the methanol oil molar ratio and the methanol hexane molar ratio were investigated to optimize the reaction conditions. The evolution of the process was followed by gas chromatography, determining the concentration of the methyl esters at different reaction times. The biodiesel was characterized by its density, viscosity, saponification value, iodine value, acidity index and water content, according to ISO norms. High methyl ester yield and fast reaction rate could be obtained even if the reaction pressure was relatively low, which is quite favorable to the production of biodiesel in industry.     

脂肪酶催化食用废油制备生物柴油

利用脂肪酶为催化剂,食用废油与甲醇反应,制备生物柴油,最佳酯化反应条件为反应温度50℃、脂肪酶催化剂用量为原料量的3%、甲醇与食用废油体积比为3∶1、共溶剂丁酮量为甲醇量的1/6、pH=7,反应时间4h,生物柴油产率可达到78%,对产品的各项指标测定,均达到GB/T20828-2007要求,指标并与0#石化柴油相接近。     

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.