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Contents lists available at ScienceDirect Energy Conversion and Management journal homepage: www.elsevier.com/locate/enconman Review Biodiesel from waste frying oils: Methods of production and purification Jhessica Marchini Fonsecaa, Joel Gustavo Telekenb, Vitor de Cinque Almeidaa, Camila da Silvac,⁎ a Departamento de Química, Universidade Estadual de Maringá (UEM), Av. Colombo, 5790, 87020-900 Maringá, PR, Brazil bDepartamento de Engenharia e Ciências Exatas, Universidade Federal do Paraná (UFPR), R. Pioneiro 2153, Palotina, PR 85950-000, Brazil c Departamento de Tecnologia, Universidade Estadual de Maringá (UEM), Av. Ângelo Moreira da Fonseca 180, Umuarama, PR 87506-370, Brazil A R T I C L E I N F O Keywords: Waste frying oil Biodiesel Purification Catalysis Dry washing Patent A B S T R A C T Waste frying oils (WFO) are a promising source in terms of feedstock for biodiesel production, and have a lower cost than the typical refined vegetable oils. In addition, the use of WFO is an environmentally correct way to use this residue; it also decreases the food versus fuel competition. However, the application of WFO has some limitations, including their high free fatty acid and water content, which influences the final ester yield in the base catalyzed reactions. This review article introduces a state-of-the-art use of WFO as feedstock for biodiesel production. Here, catalytic and non-catalytic methods are reported and discussed, and the advantages and disadvantages of using WFO are presented. Furthermore, techniques for the purification of biodiesel are dis- cussed along with patents and potential future work available in terms of production and purification. 1. Introduction Biodiesel is a biofuel derived from vegetable oils and/or animal fats. It is non-toxic, biodegradable and produces less sulfur and hydro- carbons, and can be used in diesel engines with minimal modifications [1,2]. Biodiesel consists of a mixture of monoalkyl esters and long chains of fatty acids derived from different types of oils and fats, ob- tained mostly via transesterification with a lower alcohol in the pre- sence of a catalyst [3]. Edible vegetable oils, such as soybean, sunflower and palm oils, are the main feedstock used in the production of bio- diesel. However, the high cost of these oils, which accounts for about 70% of the total value of biodiesel production, as well as the compe- tition with food and soil degradation due to large planting scales, are disadvantages for production and commercialization of biodiesel [4,5]. Waste frying oils (WFO) is considered a promising alternative in biodiesel synthesis, due to their low cost and high availability. In ad- dition, WFO use reduces competition with food demand. The cost of WFO is two to three times lower than refined vegetable oils. Their use would also reduce the costs of removal and treatment of this residue [6–9]. On the other hand, WFO contains other compounds in addition triacylglycerols, due to chemical reactions during the food cooking process or raw food. These compounds include water, free fatty acids (FFA), polar compounds and non-volatile compounds that mainly affect homogeneous catalytic transesterification reactions [10,11]. In the production of biodiesel from WFO, it is necessary to point out that some compounds formed during the cooking process are unreactive, due to their greater polarity (polymers, dimers) than the triglycerides. As a result, the percentage of FAME (fatty acid methyl ester) are lower at the end of the reaction [12,13]. In addition, polar compounds present in biodiesel negatively affect the efficiency of the engines, which is potentially problematic in terms of fuel injection and combustion [11,14,15]. The transesterification reaction to obtain biodiesel on an industrial scale is usually carried out using a homogeneous catalysis with a strong catalytic base. This reaction has advantages such as: lower reaction time, higher conversion, and a relatively small amount of catalyst used, when compared to other catalytic methods [16]. However, this homo- geneous, basic catalysis is affected mainly by the presence of FFA and water, which leads to the formation of soap and consequently reducing the yield reaction. [17]. Acid-catalyzed reactions (sulfuric acid, hy- drochloric acid), on the other hand, are not influenced by the presence of FFA. However, they are sensitive to the presence of water, and as such, their reactions are slower and require higher temperatures [16,18]. Another type of catalysis uses heterogeneous catalysts, which can be acidic and basic, enzymatic and recently ionic liquids. Heterogeneous acidic and basic catalysts are advantageous due to theirs low costs, recyclability, and the ability to simultaneously undergo esterification and transesterification. However, the heterogeneous catalysis is dis- advantageous because it has low concentration of active sites and problems of diffusion limitations, reducing reaction rates [20,21]. En- zyme-catalyzed reactions can promote esterification of FFA and https://doi.org/10.1016/j.enconman.2019.01.061 Received 5 December 2018; Accepted 19 January 2019 ⁎ Corresponding author. E-mail address: camiladasilva.eq@gmail.com (C. da Silva). Energy Conversion and Management 184 (2019) 205–218 0196-8904/ © 2019 Elsevier Ltd. All rights reserved. T http://www.sciencedirect.com/science/journal/01968904 https://www.elsevier.com/locate/enconman https://doi.org/10.1016/j.enconman.2019.01.061 https://doi.org/10.1016/j.enconman.2019.01.061 mailto:camiladasilva.eq@gmail.com https://doi.org/10.1016/j.enconman.2019.01.061 http://crossmark.crossref.org/dialog/?doi=10.1016/j.enconman.2019.01.061&domain=pdf transesterification of triacylglycerols simultaneously. Despite the easy separation of the catalyst products, the high cost and the deactivation of the enzymes remain an obstacle [22,23]. Ionic liquids are considered a new generation of catalysts, as they can act in the esterification and transesterification of the oils and are easily separated. Although they have good catalytic activity, the conditions necessary for those reac- tions are considered dangerous due to the higher temperatures and pressures [24,25]. Reactions under pressurized conditions without the presence of a catalyst have been also reported in the literature. Among the ad- vantages of these types of reactions are fast rates, decreases in mass transfer limitations, no required purification processes and simulta- neous esterification and transesterification. However, these reactions require high molar ratios of alcohol to oil and thus have a high energy cost [26–28]. The mixture of products of transesterification is composed of esters, glycerol, alcohol, monoglycerides and diglycerides, depending on the type of reaction and catalyst. The transesterification reaction is shown in Fig. 1. The purity level of the esters has a great impact on the quality of the biofuel. The process most commonly used in the removal of impurities from biodiesel is known as wet washing [29,30]. The drawback of this process is that large volumes of contaminated liquid effluents are generated; three liters of water is consumed on average per one liter of biodiesel produced [31,32]. As a way to reduce the pro- duction of these effluents, adsorption stands out as fast and low-cost dry washing method [33]. Several adsorbents composed of silica were de- veloped for the purification of biodiesel. However, this method may become impracticable due to the cost of the adsorbent [34,35]. In any case, agro-industrial waste with silica in its structure can be used as a substitute for commercial adsorbents [36,37]. This work presents a review on the potential of WFO as feedstock for biodiesel production. The article explores the main chemical reactions that occur during the cooking process, the main literature that describes using WFO with different production methods in obtaining biodiesel, the purification methods used and the published patentson production and purification steps. 2. Biodiesel Diesel engines are considered the most efficient in terms of internal combustion and cost. They also emit relatively low levels of carbon dioxide, but emit high levels of particulates and oxides of nitrogen (NOx) [38]. As an alternative to diesel oil, biodiesel has been in- vestigated by several researchers [39–43]. Biodiesel is a mixture of alkyl esters of long chain fatty acids derived from different vegetable oils and animals fats [3]. Its main character- istics are biodegradability, low sulfur content, no aromatic compounds, a high flash point, characteristic lubrication, miscibility with petroleum diesel in any mixing ratio, higher cetane number and higher oxygen content (10 to 11 wt%) in relation to petrochemical diesel. However, to improve the performance of biodiesel use, it is necessary to reduce its NOx emission levels, improve its oxidative stability, cold flow proper- ties and decrease kinematic viscosity values and density [44,45]. These improvements are important, as the use of biodiesel has less of an en- vironmental impact, reducing the dependence on fossil fuel resources greenhouse gas emissions [46]. The esters of fatty acids present the corresponding fatty acid profile of the feedstock from which it was obtained. Its major fatty acids are Fig. 1. Transesterification reaction. J.M. Fonseca et al. Energy Conversion and Management 184 (2019) 205–218 206 straight-chain, commonly with 16 to 18 carbon atoms. However, some raw materials contain substantial amounts of other fatty acids. In ad- dition to esters, the final biodiesel product includes other compounds which are limited by quality standards. These quality standards include standards D6751 of ASTM (American Society for Testing and Materials), European Standard EN 14214 and the standards of other countries [47]. Table 1 shows the main parameters evaluated in this study and their respective limits in order to ensure the quality of bio- diesel produced. 3. Characteristics of waste cooking oil Soybeans are one of the main feedstocks used as a substrate in the production of biodiesel. They have a very specific crop and are pro- duced in several regions of the world. In Brazil, for example, in the 2016/2017 harvest, approximately 3 million m3 of biodiesel were produced from soybean oil, representing 77% of the total annual yield [49]. However, biodiesel obtained from refined edible oils increases the final cost of biodiesel, in addition to competition between food versus fuel [4]. As such, oils that have already been used in frying have be- come a promising source as a substrate for biodiesel production. Fast food companies and industrial processing plants generate large quan- tities of oils. The final amounts of these oils are constantly investigated; in Brazil alone, the annual production of waste oils and fats reaches up to 1.2 million tons [50]. In some cases, these oils are mixed in animal feed, makeup and fertilizer. However the vast majority of waste oils are dumped into sewage networks [51]. Frying is defined as the immersion of foods in oils or fats at high temperatures (150 to 200 °C) in the presence of oxygen, moisture, pro- oxidants and antioxidants of food [52,53]. The heating process leads to the formation of various compounds, which vary according to the composition of the oil and food [54,55]. During the frying process several reactions may occur, including oxidation, hydrolysis, poly- merization, isomerization and decomposition of the oil into several volatile compounds [56]. The oxidation reaction occurs in the lipid, forming FFA, conjugated dienes and trienes, peroxides and by-products such as alcohols, ketones and aldehydes. The reaction rate of primary oxidation is influenced by temperature, time of exposure, light, oxygen and oil type. Peroxide is one of the main reactive byproducts of oxidation; it reaches a peak level and gradually decreases, decomposing into other compounds, in- dicating secondary oxidation [52]. Oils have high concentration of vi- tamin E, an antioxidant compound, which is lost during the frying process along with the oxidation of unsaturated fatty acids [57]. Another type of reaction that may occur is hydrolysis, which may have either a negative or positive effect on the characteristics of the oil. Water from food increases the acidity of the medium, but this water can serve as a physical barrier forming a steam layer over the oil, reducing the oxidation efficiency [58]. Furthermore, in hydrolysis, the formation of monoacylglycerols, diacylglycerols and glycerol occurs [59]. Hydrolysis and oxidation are largely responsible for the formation of polar compounds, including free fatty acids, monoacylglycerols, diacylglycerols, polymers and oxidized compounds. Polar compounds in frying oils are one of the main parameters for evaluating oil quality and reliability, as they are degradation products of the fatty acids with a maximum of 25 wt% of WFO composition [11,60]. Polymerization of oil occurs when it is heated repeatedly at elevated temperatures. Together with the polymers, there is formation of non- volatile polar compounds and triacylglycerol dimers. The amount of these compounds that is formed varies according to the type of oil. The increase in these compounds accelerates oil degradation, increases viscosity, reduces heat transfer, produces foam during the frying pro- cess and develops an undesirable color to the food. In addition, the polymers may assist in the absorption of oil by food [61]. Various other compounds are formed during frying, such as oxidized monomers of triacylglycerol, sterol derivatives, nitrogen and heterocyclic compounds containing sulfur and acrylamide [59]. The WFO can present a very varied composition due to the cooking processes. Table 2 shows the composition of WFO reported in the literature. The WFO have a very varied composition with respect to water and FFA contents. The com- position in fatty acids also varies considerably, since the types of oils used for cooking are diverse (soybean, canola, corn). The saponification values, although varying, are close to one another. As already mentioned, WFO may contain various non-convertible compounds in alkyl esters, whose maximum yield within the esters will not reach 100%. Gonzalez et al. [62] reported that in order to achieve maximum conversion, it was necessary to determine the “convert- ibility” of the oil, which consists of a quantitative analysis that de- termines the percentage of convertible and non-convertible compounds. Table 1 Biodiesel specifications and their limits. Properties EN 14214 ASTM - D6751 Composition of Biodiesel C12-C22 C12-C22 Esters Content greater than96.5% (m/m) – Density at 15 °C 860–900 kgm−3 – Viscosity at 40 °C 3.5–5.0mm2 s−1 1.9–6.0mm2 s−1 Flash Point ≥ 101 °C ≥ 130 °C Sulphur Content ≤ 10mg kg−1 ≤ 50mg kg−1 Carbon Residue ≤ 0.3% (m/m) ≤0.05% (m/m) Cetane Number ≥ 51 ≥ 47 Sulfated Ash ≤ 0.02% (m/m) ≤ 0.02% (m/m) Water Content ≤ 500mg kg−1 ≤ 0.05% (v/v) Corrosion – 3 h Oxidative Stability 110 °C ≥ 4 h ≥ 3 h Acid Value ≤ 0.50mg KOH g−1 ≤ 0.50mg KOH g−1 Iodine Value 130 g I2/100 g – Methanol Content ≤ 0.02% (m/m) – Monoacylglycerols Content ≤ 0.8% (m/m) – Diacylglycerols Content ≤ 0.2% (m/m) – Triacylglycerols Content ≤ 0.2% (m/m) – Free Glycerin ≤ 0.02% (m/m) ≤ 0.20% (m/m) Total Glycerin ≤ 0.25% (m/m) ≤ 0.25% (m/m) Pour Point – −15 to −16 °C Phosphorus Amount ≤ 4mg kg−1 ≤ 0.001% (m/m) Cloud Point – −3 to −12 °C Adapted from Ambat et al. [48]. Table 2 Variability of WFO composition. Reference Composition FFA (%) Water content (mg kg−1) C16:0 (%) C18:0 (%) C18:1 (%) C18:2 (%) C18:3 (%) Saponification value (mg KOH g−1) Eze et al. [64] 1.53 1153 6.1 1.8 64.2 19.4 8.4 NI Mansir et al. [5] 5.5 6000 60.1 10.8 27.2 1.14 NI 187.2 Tacias-Pascacio et al. [65] 1.05 400 17.82 5.75 40.98 28.77 4.51 198.54 Gharat and Rathod [66] 2.402 NI 9.08 6.82 30.6 53.5 NI 208 Gonzalez et al. [62] 1.5 6200 11.6 3.9 25.5 51.9 4.8NI Yahya et al. [67] 1.88 2000 34.80 7.90 53.30 4.00 NI 194.40 NI – Not informed. J.M. Fonseca et al. Energy Conversion and Management 184 (2019) 205–218 207 The authors reported that the WFO employed in the work had a con- vertibility of 92.1%, so the substrate contained 7.9% of compounds that would not produce esters at the end of the reaction. Abdala et al. [63] also determined the convertibility of WFO, with 93.1% and 6.9% of convertible and non-convertible compounds, respectively. 4. Methods of preparation of biodiesel Several methods can be used to produce biodiesel, including micro- emulsions, pyrolysis and transesterification. Transesterification (alco- hololysis) is the conventional method, employed on an industrial scale, in which the obtained biodiesel can be pure or in a mixture. The re- action can be carried out in various ways, catalyzed or not. Each of these methods and their advantages and disadvantages [19] are sum- marized in Table 3. The following sections report the main studies in recent literature, using the methods described in Table 3 for the production of biodiesel using WFO as feedstock. 4.1. Homogeneous catalysis 4.1.1. Alkali The base-catalyzed transesterification reaction takes place in short (60min) reaction times, and uses sodium hydroxide and potassium (NaOH and KOH, respectively) as catalysts. These reagents have high activity, affordability and availability. NaOH is preferentially used on an industrial scale because of its low molecular weight. However, KOH is beneficial in the mixture after the reaction, because it can be reacted with phosphoric acid in the neutralization step, forming potassium phosphate, which can be applied as fertilizer. It is worth mentioning that the efficiency of this type of catalysis is directly related to the concentration of impurity within the feedstock used in biodiesel pro- duction [80]. The method is the one commonly used industrially, being estimated an energy consumption of 2326 kW for 10,000 tons/year. Although it is the most widely used method, basic catalysis has dis- advantages, such as the generation of large amounts of contaminated liquid effluent. More specifically, glycerol, the byproduct of the reac- tion, is not pure and so it is not possible to reuse the catalyst. Sodium methoxide is also used as a catalyst in the transesterification reactions, in which the reaction is completed faster than NaOH and KOH [81,82]. Furthermore, soap formation may occur depending of the feedstock used [83,84]. Oils after frying have a high content of FFA and water, making the production of biodiesel by the homogeneous alkaline cat- alysis method unfeasible. These byproducts promote the formation of soap, which reduces the yield of the reaction and hinders the process of separation and purification [17]. Çayli and Küsefoǧlu [85] carried out the WFO transesterification of WFO, which had an acidity of 6.5 mg KOH g−1 and 0.7 wt% water. That study compared the process in two stages, using NaOH as a catalyst in two reactions at room temperature. In addition, the authors evaluated the effect of the presence of water and suspended particles in the final yield. They concluded that the removal of water and particulates raises the final ester content and that the two-step process was more profit- able (94%) than only one step (73%). Chhetri et al. [86] evaluated the percentage of catalyst (NaOH) and the time in the transesterification of WFO. The catalyst concentration varied from 0.4 to 1.2%, and the use of 0.8 wt% NaOH produced 94.5% of esters in 20min of reaction. The researchers also evaluated the main parameters according to the ASTM. The main operating conditions (methanol to oil molar ratio, amount of NaOH catalyst, reaction time and temperature) in biodiesel production were investigated by Meng et al. [87]. In that study, the frying oil had an acidity of 7.25mg KOH g−1. The optimal condition was found to be a methanol to oil molar ratio of 9:1, with 1 wt% of catalyst (based on oil mass), at 50 °C for 90min. However, the ratio of 6:1 is more appropriate to the process, so the final yield was 89.8% in esters. In another study, Phan and Phan [88] used KOH as a catalyst in the transesterification of different WFO, in which the acidity varied between 0.67 and 3.64mg KOH g−1, obtaining ester yields between 88 and 90% with using molar ratios of 7:1–8: 1 (methanol to oil), temperature between 30 and 50 °C and 0.75 wt% catalyst (based in the oil mass). Bautista et al. [89] stu- died the effects of biodiesel synthesis parameters, including tempera- ture, catalyst concentration and FFA content in the oil. They found that catalyst concentration is the most important factor and temperature is the least important factor influencing the yield. Hingu et al. [90] investigated the use of sonochemical reactors in the synthesis of biodiesel from WFO, in which the oil had an initial acidity of 2.805mg KOH g−1. Different operating parameters were evaluated, such as the methanol to oil molar ratio, catalyst concentra- tion, temperature, ultrasound power and pulse on the oil conversion. The best ester yield (89.5%) was obtained using a methanol to oil molar ratio of 6:1, 1 wt% catalyst, 45 °C and 200W potency for 40min. Thanh et al. [91] used a two-step process to produce biodiesel from WFO (initial acidity of1.07mg KOH g−1 and 0.015 wt% water) in an ultra- sonic reactor. The main operational variables were evaluated and the catalyst used was KOH. At the end of the second step, there was ob- tained 99% of esters. Chen et al. [92] evaluated the WFO biodiesel synthesis that had an acidity of less than 2mg KOH g−1, with two different catalysts (NaOH and sodium methoxide). In that study, the effects of time, molar ratio and microwave power were evaluated, finding that sodium methoxide was the best catalyst, yielding close to a 98% in esters. Maddikeri et al. [93] carried out an interesterification of WFO with methyl acetate and KOH. They reported an initial acidity of 4.3 mg KOH g−1 and a maximum ester yield of 90% using a concentration of 1 wt% Table 3 Advantages and disadvantages of the methods used in the synthesis of biodiesel. Method Advantages Disadvantages Homogeneous Alkaline High yield, low cost and fast reaction rate [16] Neutralization of FFA, generation of wastewater, difficult catalyst recovery and purification of products required [68] Homogeneous Acid High yield (under certain conditions), conversion of FFA to biodiesel, low cost and medium reaction rate [69] Generation of wastewater, corrosion of equipment, difficult catalyst recovery and purification of products required [48,70] Heterogeneous Alkaline High yield, medium cost, fast reaction rate, reusability and can be used in a continuous process [71] High energy requirement, tedious catalyst preparation, catalyst leaching and low surface area [72] Heterogeneous Acid High yield, medium cost, fast reaction rate, reusability, conversion of FFA to biodiesel and can be used in continuous process [73] Low concentration of active sites, high cost of the catalyst feedstock, tedious catalyst preparation and catalyst leaching [74] Enzyme High yield, conversion of FFA to biodiesel, low energy requirements, high product purity, reusability and can be used in a continuous process [75] Inhibition by alcohols and high cost [76] Ionic Liquid Simultaneous esterification and transesterification, possibility of several functional groups and water tolerant [24] Difficult recovery and recycling methods, glycerol can accumulate on the surface and decrease catalytic activity and high temperatures required for the reaction [77] Noncatalytic No catalyst, high reaction rate, tolerant to the presence of FFA and water, simultaneous esterification and transesterification and fewer number of processing steps [78] High temperature and pressure are required, high cost of equipment and high energy consumption [79] J.M. Fonseca et al. Energy Conversion and Management 184 (2019) 205–218 208 catalyst(by weight of oil), with a methyl acetate to oil molar ratio of 12:1 at 40 °C. The transesterification of WFO (FFA and water contents were 0.24mg KOH g−1 and 1.21 wt%, respectively) using NaOH as a catalyst was investigated by Rabu et al. [94]. The reactions were con- ducted at 60 °C with stirring at 400 rpm, and varying the molar ratio, time and catalyst concentration, obtaining a 95% in esters under the best operating conditions. Banerjee et al. [95] evaluated the effect of the methanol to oil molar ratio on the esters yield, ultimately synthe- sizing biodiesel from the WFO. The other variables were kept fixed at 55 °C for 90min and NaOH was used as catalyst. When the molar ratio was 15:1, the yield reached 94% of esters. In another study, Luu et al. [96] studied the effect of the addition of a co-solvent (acetone) on biodiesel synthesis. The FFA content was 0.92% and the water content was 1231.3 mg g -1. Temperature, time, amount of catalyst and molar ratio were also assessed. The highest yield (98%) was obtained under the conditions of 1 wt% of KOH (catalyst), 20 wt% acetone, methanol to oil molar ratio of 5:1, 40 °C and a reaction time of 30min. Bilgin et al. [97] investigated the biodiesel production of WFO with ethanol and NaOH as catalyst, aiming to obtain a product with the lowest possible kinematic viscosity. The lowest kinematic value was found when using a 1.25% catalyst concentration, at 70 °C for 120min, and ethanol to oil molar ratio of 12:1. Furthermore, an experimental design was applied by El-Gendy et al. [98] to verify the interaction and potential of the main operational parameters used to obtain the highest yield in esters. In that study, the FFA content of the WFO was 1.04mg KOH g−1. The optimum conditions for higher ester (∼99%) were me- thanol to oil molar ratio of 7.54:1, 0.875wt% of KOH, 52.7 °C, a re- action time of 1.17 h with constant stirring at 266 rpm. 4.1.2. Acid The acid catalysts usually investigated in homogeneous reactions are generally sulfuric and hydrochloric acid. Reactions with acid cata- lysts are not influenced by the amount of FFA in oils. Instead, the acids are capable of simultaneously esterifying the FFA and transesterifying the triacylglycerols. However, this type of catalysis requires high molar ratios of alcohol, high catalyst concentrations and long reaction times, as the reaction is corrosive and up to 4000 times slower than that catalyzed by a base [99,100,101]. Reactions using a homogeneous acid are generally applied as a pre- treatment to acidic oils, such as WFO, in order to reduce the acidity of the medium and apply a basic transesterification. Liu et al. [102] used WFO (acidity of 68.2 mg KOH g−1) for biodiesel production and a pre- treatment step was carried out using an experimental design with radio frequency heating, evaluating the conditions of time, catalyst dose and methanol to oil weight ratio on acid-catalyzed. The condition of greatest reduction of acidity was in 8min, 3 wt% H2SO4 and methanol to oil of 0.8:1, obtaining an oil with 1.64mg KOH g−1 of acidity. Charoenchaitrakool and Thienmethangkoon [103] used a WFO for biodiesel production that contained 1 wt% FFA and 0.1 wt% water. Sulfuric acid was used as a catalyst in the pre-treatment of oil, where the best FFA reduction condition was methanol to oil molar ratio of 6.1:1, 0.68 wt% sulfuric acid, at 51 °C with a reaction time of 60min. A WFO (acidity of 17.41mg KOH g−1)was used by Patil et al. [104] and the highest yields (∼90% in esters) were found using 0.5 wt% of sul- furic acid and methanol to oil molar ratio of 6:1. 4.2. Heterogeneous catalysis 4.2.1. Alkali Heterogeneous catalysts must have chemical stability, reusability, high activity at ambient temperatures and affordability. Basic hetero- geneous catalysts are generally composed of metal oxides, alkaline zeolites and clays, and are applied in reactions that use feedstock of high purity and low content of FFA and water. These catalysts generally have more active sites than heterogeneous acid catalysts. The main disadvantage of these catalysts is associated with the leaching of the active sites after reactions, thus reducing their catalytic activity [105,106]. Oxides of TiO2-MgO were employed as catalysts by Wen et al. [107] in the transesterification of the WFO, where the initial acidity was 3.6 mg KOH g−1 and the water content was 1.9 wt%. The main op- erational variables (methanol to oil molar ratio, percentage of catalyst and temperature) were evaluated in this study. The highest ester yield (92.3%) was achieved by using 10 wt% of catalyst (based on oil mass) and methanol to oil molar ratio of 50:1 at 160 °C. The study also showed that the catalyst can be reused up to four times. Several ma- terials have been used as precursor material, such as snail shells that were calcined and applied as a basic catalyst in the production of bio- diesel from WFO. This catalyst contained an acidity of 1.948mg KOH g−1, as verified in Birla et al. al. [108]. In that study, operating con- ditions were varied in order to achieve higher yields, reaching∼87% of esters under optimized conditions. In another study, Boey et al. [109] obtained calcium oxide (CaO) from calcined shells and boilers ash from agricultural waste was used as a catalyst in the transesterification of WFO. The WFO initially had 0.86mg KOH g−1 acidity and 0.35 wt% water. The mixture of 3 wt% of the ashes with CaO decreased the re- action time from 3 h to 0.5 h, converting 99% of the FFA. Mixed oxides of Ca and Zr were prepared by Dehkordi and Ghasemi [110] in various methanol to oil molar ratios applied in the reaction of WFO with me- thanol. The initial acidity and water concentrations were 0.98mg KOH g−1 and 0.124 wt%, respectively. Under appropriate conditions (65 °C, catalyst load of 10 wt%, methanol to oil molar ratio of 30:1 and 2 h of reaction), 92.1% of esters were obtained. Yahya et al. [67] used a titanium calcium catalyst to produce bio- diesel from WFO. The oil had an acidity of 3.75mg KOH g−1 and 0.20 wt% of water. The effect of time, temperature, catalytic load (re- lative to oil mass) and methanol to oil molar ratio were evaluated. The highest ester yield (80%) was achieved using 0.2 wt% catalyst and methanol to oil molar ratio of 3:1 for 1 h at 65 °C. Potassium im- pregnated zinc oxide was used as a catalyst by Yadav et al. [111] in the reaction of WFO (acidity of 1.01mg KOH g−1) with methanol. The highest ester yield (98%) was achieved at optimized reaction condi- tions, at catalyst loading of 2.5 wt%, methanol to oil molar ratio of 18:1, 65 °C and 50min. Jung et al. [112] used different biochars to catalyze the transesterification of WFO, in which the oil had an acidity of 2.85mg KOH g−1 and 0.108 wt% of water. The temperature effect was evaluated and yield in esters greater than 95% were obtained. Catarino et al. [113] employed various materials rich in calcium (do- mestic wastes and collected from the beach) as a catalyst to produce biodiesel from WFO (acidity of 2.18mg KOH g−1). The reaction was conducted using 5 wt% catalyst (relative to oil mass), methanol to oil molar ratio of 12:1 for 2.5 h and at reflux temperature of methanol. The yield of the reaction was 65% of esters and the results showed relative stability of the catalysts. 4.2.2. Acid Heterogeneous acid catalyses are performed by inorganic, poly- meric materials and sulfonated carbons. Solid acid heterogeneous cat- alysts have the advantage over basic ones because they are less sensitive to the presence of FFA and can be applied in reactions where feedstock are of lower quality. The heterogeneous acid catalysts can be applied as a pre-treatment to reduce the FFA content, or at higher temperatures, simultaneously esterify the FFA and transesterify the triacylglycerols without soap formation, reducing purification steps and forming the purest possible glycerol. However, due to the lower activity of the acid catalyst, higher reaction temperatures are required, increasing theprocess energy consumption. Another disadvantage is associated with leaching of the catalyst, as already mentioned [105,114,115]. In one study, Cao et al. [116] employed a heteropolyacid as a cat- alyst in the transesterification reaction of WFO. They found that there was a 15.65% FFA content and 0.1 wt% water content. Both the con- centration of the catalyst and the reaction time were evaluated; in the J.M. Fonseca et al. Energy Conversion and Management 184 (2019) 205–218 209 best conditions, the authors obtained 87% of esters and the catalyst showed stability for at least 5 cycles of reuse. Several solid acid cata- lysts were used by Jacobson et al. [117] to produce biodiesel from WFO (FFA content of 15%). According to that study, zinc stearate im- mobilized on silica gel was the best catalyst, yielding 98% of esters under optimal conditions. Carbohydrate-derived catalysts were in- vestigated as catalysts in the synthesis of biodiesel from WFO by Lou et al [118]. The catalysts were carbonized and subsequently sulfonated. When simultaneous esterification and transesterification were per- formed, the starch-based catalyst showed a higher yield in esters (92%). The authors even reported the same yield after 50 cycles of catalyst reuse. In another study, Ozbay et al. [119] used acidic ion exchange resins in the esterification of WFO, with 0.47% of FFA. The increase in temperature (50 to 60 °C) and the percentage of catalyst (1 to 2 wt%) increased the conversion values. The higher FFA conversion (45.7%) was obtained for the higher surface area catalyst and the larger average pore diameter. To catalyze the transesterification reaction of WFO (with a FFA content of 15%), Komintarachat and Chuepeng [120] applied various catalysts supported with ammonium metatungstate. Effects of tem- perature, time, methanol to oil molar ratio and catalyst to oil were investigated. Under best conditions, a 97.5% in esters was obtained using an alumina carrier. The SO42-/ZrO2 superacid catalyst was used to transesterify the WFO, which had a previously reported acidity of 81.25mg KOH g−1 [121]. The authors obtained a ester yield of 93.6% when using a methanol to oil molar ratio of 9:1, 3 wt% catalyst, after 4 h at 120 °C. Furthermore, Lam et al. [122] studied a superacid sulfate tin oxide (SO42-/SnO2) catalyst and the bimetallic effect with other oxides in order to improve the catalytic effect in the transesterification of WFO (initial acidity of 5mg KOH g−1 and 0.162 wt% of water). The effect of the main reaction parameters were investigated. A yield of 92.3% in esters at 150 °C, 3% SO42-/SnO2-SiO2 catalyst, methanol to oil molar ratio of 15:1 for 3 h was obtained. In another study, Li et al. [123] used Zn1.2H0.6PW12O40 nanotubes that had Lewis and Brønsted acid sites to stimulate the transesterification of WFO. In that study, the oil contained 1 wt% water and acidity of 53.8mg KOH g−1. The zinc catalyst showed a high tolerance towards the presence of water, good catalytic performance and reusability of up to 5 times without loss of activity or efficiency and with yield above 95% in esters. Corro et al. [124] carried out a two-step process in which the WFO contained 11.69% of FFA. First, the esterification of the fatty acids was carried out with methanol catalyzed with SiO2. The experimental variables were methanol to oil molar ratio of 30:1, temperature be- tween 40 and 70 °C, catalyst mass ranging from 2 to 8% (oil mass ratio) and reaction times ranging from 1 to 8 h. In the second step, a trans- esterification was performed with methanol and NaOH. In that study, the best condition for esterification was 4% catalyst, 70 °C and 4 h of reaction. At the end of the two steps, 99.56% esters were obtained. In another study, Lam and Lee [125] applied a SO42-/SnO2-SiO2 catalyst in the transesterification of WFO (FFA content of 2.54% and water content of 0.162wt%), evaluating the effect of the methanol/ethanol mixture on the reaction. A mixture of methanol to ethanol to oil molar ratio of 9:6:1, 6 wt% catalyst, 150 °C and 1 h of reaction gave an 81.4% in es- ters. The WFO conversion with a heteropolyacid catalyst using experi- mental design was applied by Talebian-Kiakalaieh et al. [126]. In that study, when the optimal condition was a reaction time of 14 h, tem- perature of 65 °C, a methanol to oil molar ratio of 70:1 and 10wt% catalyst, there was an FFA conversion of 88.6%. Alhassan et al. [127] used nanoparticles of sulfated zirconia doped with manganese sulfate as a catalyst in the transesterification of WFO (FFA content of 17.5%), and the main parameters of the reaction were evaluated. Ester yield of 96.5% was achieved at 180 °C, 600 rpm, 3 wt% catalyst and a methanol to oil molar ratio of 20:1. The catalyst was reusable for up to six times without any loss in catalytic activity. In addition, Tran et al. [128] used sulfonated carbon as the catalyst for WFO (acidity of 2.7mg KOH g−1). The catalyst mass ranged from 5 to 15% (by weight of oil), with a temperature 90 to 150 °C, a reaction time 0.5 to 6 h, and a methanol to oil molar ratio of 9.35:1. The optimal conditions for that reaction were a temperature of 110 °C, a reaction time of 2 h, 10 wt% of catalyst. Those conditions allowed for a yield of 89.6% in esters, and in that reaction, the WFO did not receive any type of pre-treatment. Ahmad et al. [129] obtained an char-based acidic and applied in the WFO (6 wt% of FFA) catalysis. The optimum conditions were 6 wt% catalyst, methanol to oil molar ratio of 9:1, 65 °C for 130min, yielding 96% in esters. After being reused for 5 times, the catalyst still showed a ester yield of 81%. 4.2.3. Enzymatic The production of biodiesel via enzymatic catalysis has been con- sidered an ecologically correct and efficient route. The process has several advantages, including conversion of feedstock of low quality (high FFA content) and lower energy consumption. However, this type of catalysis has not been used on an industrial scale because of its high enzymatic cost, which is much higher than basic homogeneous catalysis in terms of alcohol deactivation of enzymes and conversion efficiency [75,130]. The immobilized Candida lipase was studied by Chen et al. [131] as a catalyst in the biodiesel production from WFO (acidity of 143.64mg KOH g−1). The effects of lipase percentage, solvent, water, temperature and reaction mixture flux were investigated. The higher yield condition (91.08% of esters) was composed lipase to hexane to water to oil of 25:15:10:100, at 45 °C in a flow of 1.2ml min−1. The authors further reported a yield in esters loss of∼16% that after 100 h of continuous reaction. Maceiras et al. [132] used Novozym 435 lipase to catalyze transesterification of WFO (0.04 wt% water and acidity of 1.35mg KOH g−1). The optimal condition was 10% enzyme (based on oil weight), a methanol to oil molar ratio of 25:1, 4-hour reaction time held at 50 °C, yielding 89.1% in esters. Furthermore, the Novozym 435 lipase was used by Azócar et al. [133] in order to catalyze transesterification re- actions with percentage of oil ranged from 0 to 100%, temperature of 35 to 55 °C, enzyme concentration of 3–15% (relative to the oil) and the methanol to oil molar ratio of 1.5:1 to 4.5:1. The optimal condition was methanol to oil molar ratio of 3.8:1, 45 °C, 15 wt% of lipase and 100 wt % oil, for 12 h at 200 rpm, obtaining approximately 100% esters. Gharat and Rathod [66] also used Novozym 435 lipase in the catalysis of WFO (FFA content of 2.402%) under the influence of ultrasonic ra- diation with dimethyl carbonate (DMC). That study evaluated stirring conditions without ultrasonic radiation, radiation without agitation and radiation plus agitation in addition to parameters such as temperature, stirring speed, enzymatic loading and the DMC to oil molar ratio. They reported that both shaking and ultrasonic radiation increased the yield in esters 86.61%. Razack and Duraiarasan [134] used two bacterial species to produce lipase, which worked withthe catalyst in the in- teresterification of WFO (acidity of 1.68mg KOH g−1). The catalyst mass varied from 1.5 to 2.5 g, with an methyl acetate to oil molar ratio of 10:1 to 14:1, a temperature of 30 to 40 °C and a reaction time of 48 to 72 h. The optimum condition was 2 g of catalyst, methyl acetate to oil molar ratio of 12:1, 60 h of reaction at 35 °C, yielding 93.61% in esters. 4.2.4. Ionic liquid The first application of ionic liquids (ILs) in biodiesel synthesis was performed by Wu et al. [135]. ILs are salts that are in the liquid phase at temperatures below 100 °C, have low volatility, excellent chemical and thermal stability and high catalytic activity. They have the advantages of being reused and easily separated from the reaction medium. Ionic liquids are also capable of simultaneously promoting FFA esterification and transesterification of triacylglycerols [9,136]. Their main dis- advantages are related to the high temperatures used with some ionic liquids and the possibility of deactivation due to the glycerol formed [77]. Han et al. [137] prepared a Brønsted acidic ionic liquid with an alkane sulfonic acid group as catalysts in the synthesis of biodiesel from J.M. Fonseca et al. Energy Conversion and Management 184 (2019) 205–218 210 WFO (acidity of 100mg KOH g−1). The effects of the methanol to oil to catalyst molar ratio, temperature and time were evaluated. Higher temperatures increased yields and the best methanol to oil to catalyst molar ratio was 12:1:0.06 for 4 h, obtaining 93.5% esters. In another study, an acidic polymeric ionic liquid was used by Liang [138] for simultaneous esterification and transesterification of residual oil (acidity of 45mg KOH g−1). The effect of the methanol to oil molar ratio with a fixed amount of catalyst and reaction time was in- vestigated. The ester yield was close to 99% under the best operating conditions. Another study, Yassin et al. [139] used various ionic liquids of imidazolium chloride to catalyze the transesterification of WFO, obtaining 97% of esters with a catalyst to oil ratio of 1:10 for 8 h and 55 °C. The catalyst presented good stability after 8 cycles of use, with high yields. Three acid ionic liquids were evaluated by Ullah et al. [140] in the pre-treatment to reduce the acidity of the residual oil (acidity of 4.03mg KOH g−1 and 0.140wt% of water), before carrying out a KOH catalysis. The effect of catalyst concentration (3–7.5 wt%), temperature (80–180 °C), stirring (100–700 rpm), methanol to oil molar ratio (3:1–18:1) and time (30–120min) were investigated in the es- terification. BMIMHSO4 was found to be the best catalyst because of the longer chain. 4.3. Noncatalytic with alcohol at pressurized conditions The synthesis of biodiesel using an alcohol under pressurized con- ditions and without the use of catalyst was initially proposed by Saka and Kusdiana [26]. Due to the absence of catalysts, the method is tol- erant to the presence of water and FFA, as reactions of hydrolysis, es- terification and transesterification occur simultaneously. In addition, the feedstock used may be of poor quality. The reactions are complete in minutes and there is a decrease in the mass transfer limitations since there is a better solubility between the phases (oil and alcohol) in re- lation to the other methods, which raises reaction rates [26,141,142]. The main disadvantage of this method is high energy consumption (2407 kW for 10,000 tons/year), due to high temperatures and pres- sures used in the process, which increases the final cost of the produced biodiesel [82,143]. Obtaining biodiesel from WFO with supercritical methanol without a catalyst was studied by Tan et al. [144]. The reaction parameters investigated were reaction time, temperature and the methanol to oil molar ratio; the yield was compared to the yield of a refined oil. A yield of 80% in esters was obtained under the best conditions for both the residual oil and the refined oil. Gonzalez et al. [62] investigated the production of biodiesel using WFO (acid value of 1.5 mg KOH g−1 and a water content of 0.62 wt%), without a catalyst, but with methanol and ethanol. Temperature, pressure, alcohol to oil molar ratio and addition of water were explored by the researchers. Esters yield above 80% were obtained for the two alcohols studied, though ethanol presented better results. In the work of Ghoreishi and Moein [145], WFO (with FFA and water content of 5.67% and 0.2, respectively) were used as the sub- strate in the reaction with supercritical methanol and CO2 as co-solvent. The main operational parameters were applied and 95.27% of esters were obtained under the best conditions (methanol to oil molar ratio of 33.8:1, 271.1 °C, 23.1 MPa and 20.4 min of reaction time). Abdala et al. [63] evaluated the production of biodiesel using WFO (acid value of 3.57mg KOH g−1 and water content of 0.03%) under supercritical conditions without catalyst. The operating conditions of pressure (20MPa), residence time (40min) and equal ethanol to oil mass ratio, were kept constant, and the addition of water, co-solvent (n-hexane) and ethyl esters at different temperatures were studied. The authors reported that an increase in temperature, addition of 5 wt% water, addition of 20 wt% n-hexane co-solvent and addition of up to 40 wt% of ethyl esters are favorable to the process. The optimal conditions, which include an ethanol to oil mass ratio of 1:1, 300 °C, 20MPa, 70min, and 20wt% co-solvent, yielded∼ 87% of esters. Aboelazayem [146] stu- died the production of biodiesel with supercritical methanol withoutTa bl e 4 Sp ec ifi ca ti on s of bi od ie se l fr om fr yi ng oi l ob ta in ed fr om di ff er en t m et ho ds . A rt ic le Ty pe of ca ta ly st In it ia l W at er (m g kg − 1 ) In it ia l A ci di ty (% ) D en si ty (k g m − 3 ) V is co si ty (m m 2 s− 1 ) Fl as h po in t (° C ) Po ur po in t (° C ) Es te rs (% ) A ci d va lu e (m g K O H g− 1 ) C et an e nu m be r W at er (m g kg − 1 ) Sa bu da k an d Y ild iz [1 48 ] H O A N I 2 – 4. 6 88 4 5. 82 15 5 N I 76 .8 0. 41 N I 42 2 H am ze et al .[ 14 9] H O A 0. 04 0. 32 88 0 3. 8 12 0 − 2 98 .3 0. 1 54 10 0 H in dr ya w at i et al .[ 15 0] H EA 28 00 0. 89 87 3 3. 2 16 0 N I 98 .2 0. 3 N I 20 0 M an ee ru ng et al .[ 15 1] H EA 26 ,0 00 1. 0 87 4 4. 1 N I 13 .1 97 .2 0. 3 N I 30 0 G ar dy et al .[ 15 2] H EA C ID 14 00 2. 03 89 6. 1 4. 58 15 5 N I 97 .1 0. 32 N I N I A hm ad et al .[ 12 9] H EA C ID N I 6 87 9 3. 82 14 9 − 2 N I 0. 31 N I N I C he n et al .[ 13 1] En zy m e N I 72 .1 8 89 2 9. 12 19 5 N I N I 0. 12 68 28 .5 Pa na da re e R at ho d [1 53 ] En zy m e N I 2. 38 88 2 3. 85 17 1 N I N I 0. 41 N I N I Li an g [1 38 ] Io ni c liq ui d N I 22 ,6 1 87 0 4. 2 N I N I 99 .1 N I N I 20 0 U lla h et al .[ 14 0] Io ni c liq ui d 14 00 2. 02 87 9 5. 24 17 4 N I 95 .6 5 0. 41 58 .3 N I A bo el az ay em et al .[ 14 6] N on ca ta ly ti c N I 0. 40 88 7 4. 63 16 1 − 6 91 0. 09 59 N I H O A - H om og en eo us al ka lin e; H EA - H et er og en eo us al ka lin e; H et er og en eo us ac id – H EA C ID ;N I – N ot in fo rm ed . J.M. Fonseca et al. Energy Conversion and Management 184 (2019) 205–218 211 catalyst using WFO (acidity of 0.8mg KOH g−1). An experimental de- sign was applied to evaluate the influence of temperature, pressure, residence time and the methanol to oil molar ratio. The highest yield in esters (91%) was found with the following conditions: a methanol to oil molar ratio of 37:1, 253.5 °C, 198.5 bar and 14.8 min of reaction. The molar ratio and temperature had the most significant effect on the re- action process. Fonseca et al. [147] employed the hydroesterification route in a pressurized medium without catalyst; the method includes hydrolyzing the triacylglycerols with subcritical water and subsequentesterification of the FFA with ethanol in a supercritical state to produce biodiesel from WFO (1.63% FFA and 0.12 wt% water). In both stages, the effect of temperature and residence time were evaluated. The higher temperature of the hydrolysis (320 °C) obtained the highest FFA (∼96%) in 12min. Regarding the esterification, 74% of esters were obtained at 300 °C after 10min. Table 4 presents those works in which biodiesel was produced from WFO and analyses were conducted of certain specifications that were needed in order to meet the required standards. According with this table, it is possible to observe that homogeneous catalyzed reactions are influenced by high FFA levels, reducing the final yield. The other methods are little influenced by the presence of water and FFA. 4.4. Patent overview on biodiesel production from WFO Table 5 presents the published patents in which WFO have been employed as substrate of the reaction. According to the data presented in Table 5, most patents that use WFO as feedstock in biodiesel production were developed and pub- lished in the last 10 years. Those various patents had different pro- duction and different types of catalysis, including the methods de- scribed above. In one patented study, Pan et al. [154] employed a two- step method with solid and basic solid catalysts composed of inorganic material, low cost and high catalytic efficiency, reducing production costs. The acidic solid catalyst (1.5–4%) was added to the reaction medium along with WFO and methanol, with a reaction time ranging from 2 to 5 h at a temperature of 60 to 80 °C, to decrease the acidity of the oil. The oily phase was collected and reacted with the basic solid catalyst (also 1.5 to 4%); this reaction lasted between 1.5 and 2.5 h at 60 to 80 °C. In another study, Saidina [156] also employed an acidic solid catalyst to reduce the acidity of the oil and then applied a basic solid catalyst to complete the reaction. Solid acid and basic catalysts have been used by other researchers due to their advantageous re- activity with high acid oils, which may esterify and transesterify the reaction either as a pre-treatment or in the reduction of the acidity of WFO; these types of catalysis have been seen in the Chenglai and Xiaona [160], Chuanfu et al. [168] and Li et al. [169] patents. The use of enzymes as a catalyst is also presented in the patent presented by Rethore et al. [165]. The enzymes that were used in that study were not inhibited by FFA and water and esterified the FFA present and trans- esterified the glycerides. In the system used, a membrane separator separates the glycerine, alcohol and formed water; the glycerine can then be burned for power generation to maintain the reaction. 5. Purification stage Various standards must be observed in order to maintain quality standards for the final product to be considered biodiesel. Biodiesel must not be contaminated with impurities that could damage engines by accumulating in the nozzles and forming incrustations that lead to corrosivity. Such impurities come from unsaponifiable materials pre- sent in the feedstock itself, including catalyst residues, water, glycerol and excess alcohol from the reaction. When biodiesel is obtained from WFO, other compounds will be present, such as polar compounds, di- mers, mono and diacylglycerols and FFA [170]. Impurities from the WFO, generally solid, are removed by centrifugation and/or filtration before the biodiesel production reaction [171]. These impurities need to be removed as a way to maintain the quality of biodiesel. There are several methods for removing such impurities, such as membranes [172], distillation [173] and wet washing and dry washing [174]. The work sought to deepen the technique of wet washing, one of the main techniques used in the industry today and the dry washing (adsorption) that has been investigated in the last years. 5.1. Wet washing Wet washing is the traditional method for removing impurities from biodiesel. Although the efficiency of the wet washing process is proven, the method has disadvantages, including the generation of con- taminated liquid effluents, the considerable loss of product and the formation of emulsions when biodiesel is produced from waste oils with high water content and FFA [174]. Wet washing consists of adding a fixed amount of water with gentle agitation to avoid the formation of an emulsion. The process is repeated until the water is colorless, indicating the complete removal of im- purities. The three main types of wet washing employ either deionized water, an aqueous 5% phosphoric acid solution, and a mixture of an organic solvent and water [159]. The presence of an acid in the wash is beneficial in that it aims to neutralize the catalyst and decompose the soap formed. After this process, the biodiesel is washed with water to remove the remaining impurities [175]. Predojevic [30] investigated the purification of biodiesel obtained from WFO using two washing methods: (a) use of a 5% phosphoric acid Table 5 Published patents on biodiesel production using waste frying oils. Patent Title Year Reference CN 101696372 (A) Method for preparing biodiesel by solid acid-base two-step method 2010 [154] JP 2010106065 (A) Method for promoting the use of waste cooking oil for biodiesel fuel 2010 [155] MY 145698 (A) A process for producing biodiesel from waste cooking oil 2012 [156] CN 102698813 (A) Method for preparing multifunctional solid superacid catalyst and method using waste cooking oil as raw material to synthesize biodiesel 2012 [157] CN 103421615 (A) Technology for producing biodiesel through illegal cooking oil or waste cooking oil 2013 [158] CN 102925295 (A) Method for preparing biodiesel from waste cooking oil 2013 [159] CN 103571637 (A) Method for preparing biodiesel from waste cooking oil 2014 [160] CN 104164304 (A) Novel method for preparing biodiesel under catalysis of modified resin 2014 [161] US 2014/318631 (A1) Methods and systems for converting food waste oil into biodiesel fuel 2014 [162] CN 103627742 (A) Method for preparing biodiesel through conversion of waste cooking oil by utilization of immobilized lipase 2014 [163] CN 104099184 (A) Method utilizing novel solid alkali catalysts for preparing biodiesel 2014 [164] US 2015/0031097 (A1) Mobile processing systems and methods for producing biodiesel fuel from waste oils 2015 [165] CN 105985868 (A) Method for producing novel environmental-protection biodiesel 2016 [166] CN 105567436 (A) Method for preparing biodiesel by catalyzing high-acid-value waste cooking oil and detection method 2016 [167] CN 107488519 (A) Method for preparing biodiesel through catalyzing waste cooking oil by magnetic carbon-supported acid-base 2017 [168] CN 107513472 (A) Biodiesel preparation method 2017 [169] J.M. Fonseca et al. Energy Conversion and Management 184 (2019) 205–218 212 solution and (b) use of hot distilled water. After the purification treatment, the biodiesel followed the established norms on density, kinematic viscosity, acidity and iodine concentration. The phosphoric acid wash yielded 92% esters, while the hot distilled water yielded a maximum of only 89%. In another study, Sabudak and Yildiz [148] produced biodiesel with WFO and evaluated the use of hot water to remove impurities. Despite removing impurities and increasing ester yield at the end of the washing, the products were below the minimum (96.5%) required to be classified as biodiesel. Hingu et al. [90] used a 5% phosphoric acid solution to purify biodiesel obtained from WFO. The ester content increased from 89.5 to 93.5% after washing. Distilled water and tap water were studied in the purification of biodiesel ob- tained fromWFO by Berrios et al. [176]. The results were similar for the two washes, with an increase in water content and FFA. Soap, glycerol and methanol were efficiently removed by the methods after two wa- shes. Manique et al. [33] used a 1% phosphoric acid solution and wa- shed the sample twice with hotwater. The method was efficient in removing the impurities evaluated. However the water content at the end of the process was higher than in crude biodiesel. 5.2. Dry washing Dry washing is a technique that has been used regularly in industrial plants. The process consists of the application of adsorbents, such as Magnesol®, Amberlite®, Purolite® and activated carbon, which have acidic and basic sites and attract polar substances, including glycerol and alcohol [32]. The adsorption process is the accumulation on the surface of a certain material (adsorbate) on the surface of a solid (ad- sorbent) [177]. Magnesol® was developed specifically for biodiesel adsorption. It is a synthetic commercial magnesium silicate and has shown good per- formance in the removal of impurities [178]. Ionic exchange resins such as Amberlite® and Purolite® are organic, insoluble and developed to adsorb the maximum amount of the impurities found in crude biodiesel [34]. In Sabudak and Yildiz, a Magnesol® and Purolite® ion exchange resin was used to remove impurities from biodiesel obtained from WFO [148]. The impurities were removed, and the ester yield after pur- ification in the two-step transesterification process with acid-base cat- alysis was above the minimum required by the standard. Furthermore, silica gel with anhydrous sodium sulfate was used by Hingu et al. [90]. The percentage of esters was 94.5% after purification. In another study, Paula et al. [170] produced biodiesel from WFO by conventional transesterification and performed dry washing using bauxite (alu- minum oxide compound), attapulgite and bentonite (silicon dioxide). Parameters such as glycerol, water, acidity and soap were evaluated. Bauxite stood out in the removal of glycerol, and three adsorbent ma- terials were efficient in the removal of soap. In similar research, Berrios et al. [176] used Magnesol® and ben- tonite to remove biodiesel impurities from WFO. Both the adsorbent agitation and dosage process were varied in adsorption assays to de- termine their influences on the purification. The main parameters of biodiesel standards were analyzed, with no effect on viscosity, density, glycerides and ester content. Manique et al. [33] used WFO to produce biodiesel and remove impurities with Magnesol®. These impurities, such as glycerol, potassium, water, methanol, were removed. These same authors tested the ashes of the rice husk as an adsorbent, obser- ving that it efficiently reduces the acidity, water, methanol and gly- cerol. Furthermore, activated carbons obtained from tea residues were used by Fadhil et al. [179] for adsorption of impurities from biodiesel obtained from WFO. The authors found that the activated carbon was more efficient in removing impurities than simply washing with water and silica gel; the quality of the biodiesel after purification was also better. In another study, Farid et al. [180] carried out the adsorption using a bundle-derived biosorbent in palm oil; the dosage of adsorbent in the process was evaluated and the method was compared with commercial adsorbents and washing with water. The use of 5% (wt/wt) of biosorbent presented higher rates of removal of FFA, potassium, water and a lower loss of esters when compared to other methods. Using columnar coco coir fiber, Ott et al. [181] removed impurities from biodiesel obtained from WFO. The authors evaluated the ability of the adsorbent to remove soaps, methanol, FFA, calcium, magnesium and glycerol. The material proved to be efficient in removing all im- purities. Fonseca et al. [147] used sugarcane bagasse ash to remove FFA and polar compounds from biodiesel produced from WFO. The re- searchers investigated the effects of time (1–24 h), percentage of ad- sorbent (2.5–15%) and the effect of successive beds on the removal of impurities. The equilibrium conditions were found by using 12.5% ash for 8 h. At the end of the 4th bed, ∼44% of FFA and 73% of polar compounds were removed. Agroindustrial waste can be an alternative to commercial ad- sorbents, because it has high availability, low cost and good adsorption capacity [182–184]. However, there are limited studies reported in the literature and, for the most part, biodiesel is obtained from refined oils [35,185,186,187,188]. In addition to the purification treatment after the reaction, a pre- treatment can be carried out in the WFO prior to the reaction. As al- ready mentioned, some impurities, such as solids, are removed by centrifugation and/ or filtration prior to the production of the biodiesel. In the last years, some researchers applied the adsorption method, in which the materials are agroindustrial residues, to reduce the acidity of the oil before the reaction. Ali and Anany [189] used sugarcane bagasse ash to regenerate the quality of the WFO. Several parameters of the oil were investigated. The acidity reduced from 0.88 to 0.15mg KOH g−1 after treatment. Bonassa et al. [190] also used sugarcane bagasse ash in the treatment of WFO. Was applied an experimental design, in which a reduction of 68% of the acidity was observed under the best conditions. Rice husk was used by Schneider et al. [191] in the treatment of WFO. At the optimal process conditions, 22.4 °C, 80.36 rpm and 1.61 g of adsorbent, a 63% reduction of acidity was observed. In the work of Miyashiro et al. [192] the adsorption potential of bentonite and su- garcane bagasse clay was evaluated to reduce the FFA of the WFO. The sugarcane bagasse clay had a greater reduction capacity (58%) than bentonite (50%). 5.3. Patent overview on biodiesel purification Table 6 presents patented biodiesel purification works, using dif- ferent methods to remove impurities. In relation to the purification of biodiesel obtained from WFO, there are few reports, such as in the Takaka [193], Perchtoldsdorf [194] and Gurski et al. [200] patents, which indicated that the subject is still poorly investigated and of minimal interest in related research. In those two reported patents, the authors employed the use of dry washing as a purification method. The use of water washing has declined in patent research. Most studies have employed dry washing (adsorbents) as a means of pur- ification and removal of impurities present after the reaction. The ad- sorbent materials used are formed from different types of organic and inorganic compounds. Munson et al. [195] reports a purification pro- cess that uses a column packed with adsorbent material (silica, carbon, clay, among others) to remove impurities, so that the eluted biodiesel is ready for the recovery of the alcohol used in the process. The adsorbent is then regenerated and reused. In another study, Sohling [197] pa- tented an adsorbent containing approximately 40 wt% aluminum oxide for purification of crude biodiesel. Furthermore, Wang et al. [205] applied an adsorbent material composed of wood and molecular sieves to remove glycerol from biodiesel. Melde et al. [206] used a meso- porous organosilicon material to remove glycerol and detergents from crude biodiesel. A pressurized system with carbon dioxide has also been patented by Ndiaye et al. [202] for the purpose of purifying crude biodiesel, in which 10 to 50% of CO2 is injected into the system after J.M. Fonseca et al. Energy Conversion and Management 184 (2019) 205–218 213 the reaction. In this system, the pressure is then ramped up from 5 to 20MPa at ambient temperature, forming two phases, where the upper phase would consist only of esters and alcohol and the lower phase would only contain impurities. 6. Future perspectives Biodiesel production, applying WFO as substrate, and purification processes of the same biodiesel were described in this work. The use of WFO have numerous advantages over refined oils, yet further studies that evaluate the technique and limitations of WFO must be performed. For these studies there is a need to evaluate: i) the identification of the compounds generated during the frying process, ii) the analysis of convertibilityof WFO and iii) an investigation of the best catalytic or non-catalytic reaction methods. Regarding purification methods, the dry washing process excels over the conventional process. However, it is necessary to further investigate the proposed technique in relation to lower cost materials and greater process efficiency. The analysis of these points would be important in determining both the efficiency of using WFO as a substrate in the production of biodiesel and whether the dry washing process can be used as a substitute for washing with water in the purification processes. In 2013 two revision works were carried out regarding the use of WFO for biodiesel production [6,8]. Talebian-Kiakalaieh et al. [6] presented a perspective regarding the use of heterogeneous acidic and basic catalysts, due to its main property being reuse in order to make production of biodiesel more economical. In the work of Yaakob et al. [8] the perspective was of an increase in the use of WFO in the pro- duction of biodiesel, along with pretreatment processes that reduced the water and FFA contents. The development of new catalysts that improved the reaction process was also challenged. It was verified in this review that, after 5 years, the development of heterogeneous cat- alysts, both acidic and basic, occurred in order to improve their prop- erties, especially with regard to reuse. Catalysts obtained from lower cost sources, waste, have been investigated, and reuse studies have shown a good stability of developed catalysts. WFO continues to be studied by the scientific community over the last five years, in which WFO pretreatment processes and post-reaction purification processes have been the subject of research, in which studies of a simple and inexpensive method have been presented, adsorption, which has been shown to be efficient. Acknowledgements The authors are grateful to CAPES (process: 88887.286823/2018- 00) for financial support. This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors. References [1] Baskar G, Aberna Ebenezer Selvakumari I, Aiswarya R. 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