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.     

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.     

预酯化-酯交换法利用餐饮废油脂制备生物柴油

以高酸值餐饮废油脂和乙醇为原料,采用预酯化-酯交换法制备生物柴油。第一步为预酯化反应,控制反应温度为70℃,最佳条件为:催化剂加入量为4%,反应时间为90min,带水剂加入量为10%,乙醇加入量控制在醇酸摩尔比为6∶1,可使油脂酸值降至4mg KOH·g-1以下,满足酯交换反应要求。第二步为酯交换反应,最佳条件是:醇油摩尔比为8∶1,碱性催化剂加入量为0.8%,反应温度为70℃,反应时间为30min。本方法具有反应时间短、转化率高,反应条件温和,清洁环保等优点。     

Distribution of soap in a membrane reactor in the production of fame from waste cooking oil

A continuous‐flow membrane reactor was constructed for the production of fatty acid methyl ester (FAME) from waste vegetable oil with high free fatty acid (FFA) content. FAME was produced via base‐catalysed transesterification with methanol at two FFA levels: 4.8 and 10 mass%. The effect of the ceramic membrane pore size on the separation of soap and triglycerides from the FAME in the reactor was investigated. In all cases, the triglyceride was completely retained in the reactor, yielding free and total glycerine contents in the produced FAME significantly below the maximum limits of the ASTM D6751 standard. The soaps produced in the reaction mixture were not completely retained in the reactor and did not affect the FAME production process. © 2012 Canadian Society for Chemical Engineering     

棕榈油酯交换制备生物柴油的反应动力学

在甲醇与棕榈油的摩尔比为6∶1和催化剂KOH用量为棕榈油质量1.0%的条件下,研究不同温度下棕榈油制备生物柴油的酯交换反应动力学,采用Origin软件拟合曲线方程,建立棕榈油酯交换反应的宏观动力学模型。研究结果表明:棕榈油制备生物柴油的酯交换反应遵循1.40级动力学方程,反应速率随温度的升高而加快,二者符合Arrhenius方程,该反应的活化能为27.23 kJ/mol,频率因子为1.4×103。文中研究建立的反应动力学模型将对扩大试验研究提供理论依据和基础数据支持。     

Biodiesel production from waste cooking oil in a microtube reactor

Waste cooking oil (WCO) was used to produce biodiesel in a microtube reactor. First, the acid value of the WCO was reduced from 3.96 mg KOH/g to less than 1 mg KOH/g via acid catalyzed esterification. The effects of the methanol-to-WCO molar ratio (4.5:1–18:1), the H₂SO₄ concentration (0.5–2 wt.%), reaction temperature (55–70 °C), and reaction time (5–20 s) were studied. The optimal conditions were 9:1 methanol-to-WCO molar ratio, 1 wt.% H₂SO₄, 65 °C and 5 s of reaction time. Triglycerides in the product from the first step were transesterified with methanol and alkaline catalyst. Methyl ester content of the biodiesel was 91.76%.     

CFD analysis of two‐phase turbulent flow in internal airlift reactors

The hydrodynamic performance of three internal airlift reactor configurations was studied by the Eulerian–Eulerian k–ε model for a two‐phase turbulent flow. Comparative evaluation of different drag and lift force coefficient models in terms of liquid velocity in the riser and downcomer and gas holdup in the riser was highlighted. Drag correlations as a function of Eötvös number performed better results in comparison to the drag expressions related to Reynolds number. However, the drag correlation as a function of both Reynolds and Eötvös numbers fitted well with experimental results for the riser gas holdup and downcomer liquid velocity in configurations I and II. Positive lift coefficients increase the liquid velocity and decrease the riser gas holdup, while opposite results were obtained for negative values. By studying the effects of bubble size and their shape, the smaller bubbles provide a lower liquid velocity and a gas holdup. The effects of bubble‐induced turbulence and other non‐drag closure models such as turbulent dispersion and added mass forces were analysed. The gas velocity and gas holdup distributions, liquid velocity in the riser and downcomer, vectors of velocity magnitude and streamlines for liquid phase, the dynamics of gas holdup distribution and turbulent viscosity at different superficial gas velocities for different reactor configurations were computed. The effects of various geometrical parameters such as the draft tube clearance and the ratio of the riser to the downcomer cross‐sectional area on liquid velocities in the riser and the downcomer, the gas velocity and the gas holdup were explored. © 2011 Canadian Society for Chemical Engineering     

Lipase‐catalyzed production of biodiesel from rice bran oil

Biodiesel has attracted considerable attention as an alternative fuel during the past decades. The main hurdle to the commercialization of biodiesel is the cost of the raw material. Use of an inexpensive raw material such as rice bran oil is an attractive option to lower the cost of biodiesel. Two commercially available immobilized lipases, Novozym 435 and IM 60, were employed as catalyst for the reaction of rice bran oil and methanol. Novozym 435 was found to be more effective in catalyzing the methanolysis of rice bran oil. Methanolysis of refined rice bran oil and fatty acids (derived from rice bran oil) catalyzed by Novozym 435 (5% based on oil weight) can reach a conversion of over 98% in 6 h and 1 h, respectively. Methanolysis of rice bran oil with a free fatty acid content higher than 18% resulted in lower conversions (<68%). A two‐step lipase‐catalyzed methanolysis of rice bran oil was developed for the efficient conversion of both free fatty acid and acylglycerides into fatty acid methyl ester. More than 98% conversion can be obtained in 4–6 h depending on the relative proportion of free fatty acid and acylglycerides in the rice bran oil. Inactivation of lipase by phospholipids and other minor components was observed during the methanolysis of crude rice bran oil. Simultaneous dewaxing/degumming proved to be efficient in removing phospholipids and other minor components that inhibit lipase activity from crude rice bran oil. Copyright © 2005 Society of Chemical Industry     

Spray Characteristics of Two‐phase Feed Nozzles

The present study focuses on understanding the spray characteristics of a turbulent gas‐liquid jet (Re_liq = 24,000). Air and water are used as the test fluids. The angles of injection of the two phases upstream of the nozzle are varied (θ = 20°, 45° and 90°) and the effect of carrier gas on the droplet characteristics is are also investigated. The droplet size and velocity are non‐intrusively measured using a Phase‐Doppler Particle Analyzer (PDPA). In some respects, the characteristics of the present two‐phase jet are similar to those noticed in previous studies, while revealing some important differences. The centreline mean droplet velocities (15 ～ 20 m/s) increase in the initial region of the jet, attain a maximum and then decrease at larger distances from the nozzle exit. Most of the entrainment occurs at the tip of the nozzle and the jet expansion rate decreases significantly at distances where the spray velocity profiles become self‐similar. A Lorentz‐type fit has been used to model the normalized radial velocity profiles. The results indicate that the test configuration with θ = 45° may be beneficial for the scenario discussed.     

废油脂预处理及制备生物柴油研究进展

介绍了废油脂的预处理工艺及我国废油脂的现状,重点阐述了国内外以废油脂为原料经碱法、酸法和酶法酯交换制备生物柴油的研究情况,并对目前存在的问题和相应的解决对策进行了简单的讨论。     

Synthesis of biodiesel from sunflower oil with silica‐supported NaOH catalysts

BACKGROUND: A series of NaOH catalysts supported on commercial silica have been prepared by conventional incipient wetness impregnation and their activity tested in the reaction of transesterification of refined sunflower oil with methanol at 323 K and atmospheric pressure. The effects of the molar methanol/oil ratio, catalyst concentration, NaOH loading and calcination of the supported catalysts have been investigated. RESULTS: It has been found that the transesterification rate largely depends on the catalyst/methanol ratio and that calcination of the NaOH catalysts supported on silica, even at moderate temperatures, had a very negative effect on their activity. Selectivity, on the other hand, is more affected by the methanol/oil ratio. Selectivity for methyl esters (biodiesel) improved with the methanol/oil ratio due to an increased transesterification rate of diglycerides, whereas the selectivity for monoglycerides was not affected. CONCLUSION: The NaOH/silica catalysts suffered from a significant lack of chemical stability under reaction conditions as evidenced by measurements of sodium extracted during the reaction progress; therefore, their performance was affected by the presence of Na dissolved in the methanol phase. Copyright © 2008 Society of Chemical Industry     

Single‐step ultrasonic synthesis of biodiesel from crude Jatropha curcas oil

A novel single‐step process with chlorosulfonic acid catalyst for ultrasonic biodiesel synthesis using feedstock with high free fatty acid content is investigated.Jatropha curcas oil has been used as the model feedstock with methanol as alcohol. The distinct merit of chlorosulfonic acid is that it catalyzes both esterification and transesterification reactions. Moreover, chlorosulfonic acid also counteracts inhibition caused by water formed during esterification, which is the cause for very slow kinetics of acid catalyzed transesterification. In addition, sonication of the reaction mixture also causes strong micromixing and emulsification that enhances the transesterification kinetics. Statistical optimization of the process shows 93% yield for 8.5 wt % catalyst, 20:1 alcohol to oil molar ratio and temperature of 333 K. Peculiar feature of this process is that high yield is seen at moderate temperature and molar ratio, which are much smaller than that for conventional sulfuric acid catalyzed processes. The activation energy for the process (57 kJ/mol) is at least 3× lower than the energy for sulfuric acid catalyzed transesterification. The thermodynamic analysis reveals that the net Gibbs energy change for the single‐step process is almost same as that for sulfuric acid catalyzed process. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1572–1581, 2014     

棉籽油制备生物柴油的多组分体系的溶解度

研究了以棉籽油为原料制备生物柴油过程中,多组分体系之间的溶解度关系。分别测得在20℃、40℃、60℃下,甲醇 甲酯 棉籽油、甲醇 四氢呋喃 棉籽油、甲醇 甘油 棉籽油、甲醇 甲酯 甘油、棉籽油 甲酯 甘油5个三组分体系的相图。结果表明,生成的甲酯和加入的四氢呋喃都可促使甲醇和棉籽油互溶,使反应均相进行。副产物甘油在反应相中的溶解度小,有利于提高转化率。     

废食用油脂固定床酶法合成生物柴油研究

利用废食用油脂合成生物柴油,既能够实现废弃物的清洁利用,又能提供可再生的绿色能源。采用固定化假丝酵母脂肪酶为催化剂,在三级固定床反应器内,采用分级流加甲醇的方式,每级醇油摩尔比为1∶1,探讨了酶质量分数、溶剂质量分数、水质量分数、温度、反应液流速等与产物中甲酯质量分数的关系。实验结果表明,当油中酶、溶剂、水的质量分数分别为25%,15%,10%,反应液流速为1.2 mL/min,温度为45℃时,产物中甲酯质量分数达到最大值91.08%,其中油酸甲酯质量分数最高。产品经过精制后,理化性质符合美国和德国生物柴油标准,绝大多数指标优于我国0#柴油。     

制备活性炭负载K2CO3用于催化餐饮废油合成生物柴油

以K₂CO₃为催化剂,工业碱木质素(KL)为活性炭(AC)前体,在管式电阻炉中经一步共混活化(K₂CO₃/KL质量比为0.6、活化温度800℃、N₂流量100cm³/min、活化时间2h)制备K₂CO₃/AC固体碱催化剂,用于餐饮废油与甲醇的酯交换反应合成生物柴油。对制备的固体碱催化剂进行了X-射线衍射(XRD)、BET表面积及扫描电镜(SEM)表征。考察了反应温度、催化剂用量、反应时间、醇油摩尔比等因素对餐饮废油转化为生物柴油产率的影响。结果表明当反应时间2h、反应温度60℃、醇油摩尔比15:1、催化剂为原料油质量的3.0%时,生物柴油最大产率为87.5%。考查了催化剂的循环利用效果,结果表明催化剂能循环利用3次,第3次利用时生物柴油的产率仍达到80.7%。