Production of biodiesel from palm fatty acid distillate using sulfonated-glucose solid acid catalyst:Characterization and optimization

A palm fatty acid distillate (PFAD) has been used for biodiesel production. An efficient sulfonated-glucose acid catalyst (SGAC) was prepared by sulfonation to catalyze the esterification reaction. The effect of three variables i.e. methanol-to-PFAD molar ratio, catalyst amount and reaction time, on the yield of PFAD esters was studied by the response surface methodology (RSM). The optimum reaction conditions were:12.2:1 methanol-to-PFAD molar ratio, 2.9%catalyst concentration and 134 min of time as predicted by the RSM. The reaction under the optimum conditions resulted in 94.5%of the free fatty acid (FFA) conversion with 92.4%of the FAME yield. The properties of the PFAD esters were determined according to biodiesel standards.     

Modeling of the nanocrystalline-sized mesoporous zinc oxide catalyst using an artificial neural network for efficient biodiesel production

The sulfonated mesoporous zinc oxide catalyst (SO₃H–ZnO) was hydrothermally fabricated and functionalized by sulfonation to catalyze the palm fatty acid distillate (PFAD) to esters. The effect of different reaction parameters including reaction time, reaction temperature, metal ratio, and calcination temperature was modeled by artificial neural networks (ANNs) to find out the possible relative optimum conditions of the synthesized mesoporous SO₃H–ZnO catalyst for the prediction of the nanocrystalline size. Under the optimized conditions of calcine temperature 700?°C, 18?min reaction time, 160?°C reaction temperature, and 4?mmol of Zn concentration predicted a 56.41?nm size of the mesoporous SO₃H–ZnO catalyst. The acquired model was statistically verified for its utility. The quick propagation model with four nodes in the input layer, six nodes in the hidden layer and one node in the output layer (QP-4-6-1) was chosen as the final model due to its optimum statistical characteristics. Furthermore, the most effective parameter was found to be the zinc concentration whilst the reaction time demonstrated the least influence. The optimized mesoporous SO₃H–ZnO catalyst was further utilized for esterification of PFAD, depicting a high fatty acid methyl ester yield (96.11%). It shows a valuable application for the conversion of discarded oils/fats containing high free fatty acids for the production of renewable green biodiesel.     

Biodiesel production by direct methanolysis of oleaginous microbial biomass

Biodiesel is a renewable fuel conventionally prepared by transesterification of pre‐extracted vegetable oils and animal fats of all resources with methanol, catalyzed by strong acids or bases. This paper reports on a novel biodiesel production method that features acid‐promoted direct methanolysis of cellular biomass of oleaginous yeasts and filamentous fungi. The process was optimized for tuning operation parameters, such as methanol dosage, catalyst concentration, reaction temperature and time. Up to 98% yield was reached with reaction conditions of 70 °C, under ambient pressure for 20 h and a dried biomass to methanol ratio 1:20 (w/v) catalyzed by either 0.2 mol L^?1 H₂SO₄ or 0.4 mol L^?1 HCl. Cetane numbers for these products were estimated to range from 56 to 59. This integrated method is thus effective and technically attractive, as dried microbial biomass as feedstocks omits otherwise tedious and time‐consuming oil extraction processes. Copyright © 2007 Society of Chemical Industry     

Carbohydrate-derived Solid Acid Catalysts for Biodiesel Production from Low-Cost Feedstocks: A Review

Currently, most biodiesels are produced from virgin vegetable oils using a transesterification reaction. However, there are a number of other potential cheap sources for biodiesels, such as deep-frying oils/fats and palm fatty acid distillate (PFAD). PFAD is a lower-value by-product of the palm oil industry and is an economical source for biodiesel production. Due to the high cost of biodiesel production, the formulation of a new method to produce a cheaper biodiesel is imperative. Low-quality feedstocks (especially PFAD) using green and highly reusable catalysts have gained popularity due to their low production cost. High free fatty acids (HFFA) in the feedstock causes problems during the biodiesel production process, especially with the use of basic heterogeneous and homogenous catalysts. Recently, the effectiveness of a solid acid catalyst to catalyze biodiesel production from HFFA feedstock has caught the attention of researchers.

This comprehensive article explores the use of low-quality feedstocks and carbon-based catalysts for the conversion of a waste refinery crude palm oil product which contains a high percentage of FFA. The production and characterization of carbohydrate-derived solid acid catalysts are discussed, including their physico-chemical property measurements. Techniques used for the synthesis of biodiesels are also included. In addition, transesterification process variables such as the oil/methanol molar ratio, catalyst concentration, reaction time, and temperature are investigated. The final part of the article contains the combustion, emissions, and performance of produced biodiesels. Finally, conclusions, including perspectives and future developments, are also presented. The aim of this article is to demonstrate the current state of the use of low-quality feedstocks and green heterogeneous solid acid catalysts for the use in biodiesel production.     

Production of Methyl Oleate in Reactive‐Separation Systems

The esterification of oleic acid and methanol using sulfuric acid as a homogeneous catalyst is studied in reactive‐separation systems. The conversion of the free fatty acid was investigated in two different experiments with the molar ratio of methanol/oleic acid, amount of catalyst, temperature, and reaction time as variables. The conversion of the free fatty acid was found to depend strongly on the molar ratio of methanol/oleic acid. The reaction time had a direct effect on the conversion of the free fatty acid, and this conversion decreased with higher temperature. These results were valuable for a preliminary study on biodiesel production, using an acid homogeneous catalyst in a reactive dividing‐wall distillation column.     

负载型固体酸催化合成生物柴油

以固体酸TSOH/HY-SBA-15（对甲苯磺酸改性的介孔分子筛）为催化剂,催化大豆油和甲醇制备生物柴油,考察了反应的最适宜条件。结果表明,催化剂为(0.5 mol/L)TSOH/(10 %)HY-SBA-15,反应温度为180 ℃,反应时间为7 h,n(醇)/n(油)为25,催化剂用量为油质量的5 %,溶剂用量为油质量的30 %,生物柴油的收率可达到94.6 %。     

Biodiesel Production from Soybean Oil Catalyzed by Li<Subscript>2</Subscript>CO<Subscript>3</Subscript>

In the present study, we synthesized biodiesel from soybean oil through a transesterification reaction catalyzed by lithium carbonate. Under the optimal reaction conditions of methanol/oil molar ratio 32:1, 12 % (wt/wt oil) catalyst amount, and a reaction temperature of 65 °C for 2 h, there was a 97.2 % conversion to biodiesel from soybean oil. The present study also evaluated the effects of methanol/oil ratio, catalyst amount, and reaction time on conversion. The catalytic activity of solid base catalysts was insensitive to exposure to air prior to use in the transesterification reaction. Results from ICP-OES exhibited non-significant leaching of the Li₂CO₃ active species into the reaction medium, and reusability of the catalyst was tested successfully in ten subsequent cycles. Free fatty acid in the feedstock for biodiesel production should not be higher than 0.12 % to afford a product that passes the EN biodiesel standard. Product quality, ester content, free glycerol, total glycerol, density, flash point, sulfur content, kinematic viscosity, copper corrosion, cetane number, iodine value, and acid value fulfilled ASTM and EN standards. Commercially available Li₂CO₃ is suitable for direct use in biodiesel production without further drying or thermal pretreatment, avoiding the usual solid catalyst need for activation at high temperature.     

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.     

Esterification of palm fatty acid distillate (PFAD) in supercritical methanol: Effect of hydrolysis on reaction reactivity

This study demonstrated the potential use of local palm fatty acid distillate (PFAD) as alternative feedstock for fatty acid methyl esters (FAMEs) production and the possibility to replace the conventional acid-catalyzed esterification process (with H₂SO₄), which was industrially proven to suffer by several corrosion and environmental problems, with non-catalytic process in supercritical methanol. At 300 °C with the PFAD to methanol molar ratio of 1:6 and the reaction time of 30 min, the esterification of PFAD in supercritical methanol gave FAMEs production yield of 95%. Compared with transesterification of purified palm oil (PPO) in supercritical methanol, the production of FAMEs reached the maximum yield of only 80% at 300 °C with higher requirement for methanol (1:45 PPO to methanol molar ratio). Compared with the conventional acid-catalyzed esterification of PFAD, only 75% FAMEs yield was obtained in 5 h. The presence of water in the feed (between 0 and 30% v/v) was found to lower the yield of FAMEs production from PFAD significantly. This negative effect was proven to be due to the further hydrolysis of FAMEs, which nevertheless can be minimized when high content of methanol was used.     

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。     

固体碱催化黄连木籽油制备生物柴油

制备了K2CO3/Mg(A l)O固体碱催化剂,适宜制备条件为:K2CO3负载量30%、在700℃下焙烧4 h。用比表面积测定仪、X射线衍射仪、红外光谱仪对其进行了表征。以黄连木籽油为原料,开展了酯交换法制备生物柴油的研究,考察了主要影响因素:醇油摩尔比、催化剂用量、反应时间和反应温度对酯交换反应的影响,得到的酯交换反应适宜条件为:以黄连木籽油0.01 mol计,醇油摩尔比12∶1、催化剂用量为黄连木籽油质量的4.0%、反应时间2.5 h、反应温度68℃。在该条件下生物柴油的收率可达99%以上。催化剂经4次循环使用,生物柴油收率仍可保持在96%以上。用FTIR1、HNMR对所制备的产品进行了表征,证明产品中含有饱和脂肪酸甲酯和不饱和脂肪酸甲酯。     

Feasibility Study of Microwave-Assisted Biodiesel Production from Vegetable Oil Refinery Waste

Vegetable oil refinery waste containing acid oil is used as an inexpensive feedstock for producing biodiesel by microwave-assisted esterification (MAE) method. Effects of some main variables such as free fatty acid:methanol molar ratio (1:1, 1:5, and 1:10), reaction time (5, 30, and 60 min), and catalyst concentration (1%, 2%, and 3%) on physicochemical properties of produced biodiesel are investigated. Optimum reaction conditions of MAE are free fatty acid:methanol molar ratio of 1:10, reaction time of 60 min, and a catalyst concentration of 3%, while having 95.79% conversion yield. By increasing the conversion yield of the biodiesel, density and color brightness increase, while viscosity and refractive index decrease. There are no significant differences between physicochemical and heating properties of biodiesel produced by MAE and magnetic stirrer esterification (MSE) methods. Meanwhile, energy consumption of MAE method is almost four times lower than that of MSE. MAE as a promising alternative to the conventional esterification method can be considered as an energy-efficient method for producing biodiesel from inexpensive vegetable oil refinery waste. Practical applications : Acid oil is an inexpensive by-product of alkali refining in vegetable oil plants that would pollute the environment if not rendered safely. In this study, MAE is used to convert acid oil to biodiesel as a practical process for bringing alkali refining waste into production cycle. Acid oil can provide a reduction in the cost of biodiesel production. In addition, application of energy-efficient MAE method can facilitate the economical production of biodiesel.     

Biodiesel Synthesis from Palm Fatty Acid Distillate Using Tungstophosphoric Acid Supported on Cesium-Containing Niobia

Tungstophosphoric acid supported on cesium-containing niobia (TPA/Cs _x /Nb₂O₅, x = 1.0–2.5) catalysts were prepared by a two-step impregnation method, and their physico-chemical properties were investigated. The initial studies on the esterification of oleic acid with methanol revealed that TPA/Cs ratio affected the acidity as well as the activity of the catalysts. Among the catalysts tested, TPA/Cs_1.0/Nb₂O₅ exhibited the best performance. In addition, the efficiency of TPA/Cs_1.0/Nb₂O₅ for biodiesel synthesis from palm fatty acid distillate (PFAD), a by-product from palm oil industry, was demonstrated, and the reaction parameters were also evaluated. Over 90% yield of FAME was achieved, and the properties of the biodiesel obtained from PFAD met the standard requirements for biodiesel fuel. However, deactivation of the catalysts was observed, possibly due to structural transformation or organic residues blocking the active sites.     

Esterification of Palm Fatty Acid Distillate Using a Sulfonated Mesoporous CuO‐ZnO Mixed Metal Oxide Catalyst

A nanocrystalline mesoporous CuO‐ZnO hollow sphere was successfully fabricated by the hydrothermal method. The nanocomposite was formed in the presence of polyethylene glycol as a dispersant and D‐glucose as a template. The mesoporous CuO‐ZnO catalyst was further functionalized with benzenesulfonic acid to catalyze the esterification of palm fatty acid distillate (PFAD). The physicochemical, textural, structural, and thermal properties of the mesoporous CuO‐ZnO mixed‐oxide catalysts were evaluated. The modified mesoporous catalyst possessed unique textural properties. With a Cu/Zn atomic ratio of 1.0 the best catalytic activity through PFAD esterification was achieved. The optimum reaction conditions in terms of methanol/PFAD molar ratio, catalyst concentration, reaction temperature, and reaction time were determined.     

固体超强酸SO_4~(2-)/SnO_2-SiO_2催化制备生物柴油的研究

以固体超强酸SO_4~(2-)/SnO_2-SiO_2为催化剂催化大豆油和甲醇的酯交换反应制备生物柴油,考察了催化剂的制备条件和反应的最佳条件.结果表明,当催化剂的Sn/Si摩尔比达1/3以上.浸渍硫酸溶液的浓度为1.0～1.5 mol/L,450℃焙烧5 h,该催化剂对酯交换反应有很高的催化活性.在醇油摩尔比为13:1、每摩尔油使用1.0 g催化剂、120℃反应3 h,脂肪酸甲酯的收率达90%以上.催化剂具有L酸中心和B酸中心,具有超强酸性.反应体系的水抑制催化剂的活性,但催化剂的活性不受体系中游离脂肪酸的影响,这意味着催化剂能高效催化那些未精炼原油和那些不可食用的油料,使酯化和酯交换一步完成.     

Determination of deep eutectic solvents as eco-friendly catalysts for biodiesel esterification from an alcohol-palmitic acid mixture

Deep eutectic solvents (DESs) were prepared by mixing a quaternary salt as a hydrogen bond acceptor with a hydrogen bond donor. In this study, DESs had an excellent effect as a solvent-catalyst for the esterification of palmitic acid and methanol. This method was found to be safe, mild, simple, and eco-friendly. A range of DESs with different mixing ratios were used to optimize the preparation of methyl palmitate. Other factors, such as temperature, time and DESs/methanol ratio, were also examined. The optimal DES was prepared from tetrabutyl ammonium chloride and acetic acid (1 : 2); the methanol and palmitic acid sample to DES ratio was 1 : 0.5 (v/v). The reaction was optimized at a methanol/palmitic acid ratio of 10 : 1 (mol/mol) at 60 °C for 60 min. The yield was 94.3% under the optimized conditions. Therefore, DESs can be developed as a catalyst for the esterification of palmitic acid for obtaining methyl palmitate as biodiesel, and have potential applicability in other biodiesel pretreatments.     

Magnetic Solid Base Catalysts for the Production of Biodiesel

Magnetic solid base catalysts were prepared by loading Na₂SiO₃ on Fe₃O₄ nano-particles with Na₂O·3SiO₂ and NaOH as precipitator. The catalysts were used to catalyze the transesterification reactions for the production of fatty acid methyl esters (FAME, namely biodiesel) from cottonseed oil. The optimum conditions of the catalysts' preparation and transesterification reactions were investigated by orthogonal experiments. The catalyst with the highest catalytic activity was obtained when Si/Fe molar ratio of 2.5, aging time of 2 h, calcination temperature of 350 °C, calcination time of 2.5 h. Magnetic of the catalyst was characterized with Vibrating Sample Magnetometer (VSM) and transmission electron microscopy photograph (TEM), and the results showed the catalyst Na₂SiO₃/Fe₃O₄ had good specific saturation magnetization and paramagnetism, and its water resistance was better than the traditional homogeneous base catalysts; under the transesterification conditions of methanol/oil molar ratio of 7:1, catalyst dosage of 5%, reaction temperature of 60 °C, reaction time of 100 min and stirring speed of 400 rpm, yield of biodiesel was 99.6%. The lifetime and recovery rate of the magnetic solid base catalyst were much better than those of Na₂SiO₃.     

Synthesis of biodiesel from cottonseed oil and methanol using a carbon-based solid acid catalyst

A carbon-based solid acid catalyst was prepared by the sulfonation of carbonized vegetable oil asphalt and used to catalyze the transesterification of methanol with cottonseed oil. This catalyst was characterized by scanning electron microscopy/energy dispersive spectroscopy, BET surface area and pore size measurement, thermogravimetry analysis and Fourier transform infrared spectroscopy. The sulfonated multi-walled carbon nanotubes (s-MWCNTs) was also prepared and used to catalyze the same transesterification as the asphalt catalyst. The asphalt-based catalyst shows higher activity than the s-MWCNTs for the production of biodiesel, which may be correlated to its high acid site density, its loose irregular network and large pores can provide more acid sites for the reactants. The conversion of cottonseed oil 89.93% was obtained (using the asphalt-based catalyst) when the methanol/cottonseed oil molar ratio was 18.2, reaction temperature at 260 °C, reaction time 3.0 h and catalyst/cottonseed oil mass ratio of 0.2%. Also, it can be re-used. The sulfonated polycyclic aromatic hydrocarbons provide an electron-withdrawing function to keep the acid site stable. The catalyst can substantially reduce energy consumption and waste generation in the production of biodiesel.     

硅钨酸在麻疯树油合成生物柴油中的应用研究

以麻疯树油与甲醇为原料,以硅钨酸为催化剂,通过酯交换反应制备生物柴油。考察了不同反应温度、反应时间、醇油摩尔比、催化剂质量分数等因素对生物柴油转化率的影响,并采用FT-IR和1H-NMR分别对催化剂进行了表征。研究结果表明：脱水后的硅钨酸具有较强的催化活性,其在反应温度为65℃、反应时间为3 h、醇油摩尔比为12∶1、催化剂质量分数为3.0%时,麻疯树油转化成生物柴油的转化率可达81.7%。     

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.