Grasas y Aceites 75 (1)
January-March 2024, e545
ISSN-L: 0017-3495
https://doi.org/10.3989/gya.0429231

Microwave-assisted transesterification of sour cherry kernel oil for biodiesel production: comparison with ultrasonic bath-, ultrasonic probe-, and ohmic-assisted transesterification methods

Transesterificación asistida por microondas de aceite de semilla de cereza ácida para la producción de biodiesel: comparación con métodos de transesterificación asistida por baño ultrasónico, sonda ultrasónica y óhmica

M. T. Golmakani

Department of Food Science and Technology, School of Agriculture, Shiraz University, Postal Code 71441-65186, Shiraz, Iran.

https://orcid.org/0000-0001-5173-1178

M. Niakousari

Department of Food Science and Technology, School of Agriculture, Shiraz University, Postal Code 71441-65186, Shiraz, Iran.

https://orcid.org/0000-0002-4557-9031

A. Peykar

Department of Food Science and Technology, School of Agriculture, Shiraz University, Postal Code 71441-65186, Shiraz, Iran.

https://orcid.org/0009-0003-3689-7112

T. Safaeipour

Department of Food Science and Technology, School of Agriculture, Shiraz University, Postal Code 71441-65186, Shiraz, Iran.

https://orcid.org/0009-0003-1084-0599

SUMMARY

In this study, sour cherry kernel oil was converted to biodiesel by microwave-assisted transesterification. Evaluations were made of several variables, namely, reaction time (1, 2, 3, 4, and 5 min), microwave power (100, 200, 300, 400, and 500 W), methanol/oil mole ratio (3, 6, 9, 12, and 15), and catalyst (KOH) concentration (0.3%, 0.6%, 0.9%, 1.2%, and 1.5%). The efficiency of fatty acid methyl esters increased in response to lengthier reaction times, greater microwave power, higher methanol/oil mole ratio, and higher catalyst concentrations up to the optimal level. The optimal reaction conditions for microwave-assisted transesterification were 300 W microwave power, 1.2% catalyst concentration, a methanol/oil mole ratio of 1:2, and a reaction time of 4 min. Microwave-assisted transesterification was more effective than ohmic-, magnetic stirrer-, ultrasonic probe-, and ultrasonic bath-assisted transesterification methods. In conclusion, microwave-assisted transesterification can be suggested as a fast, efficient, and economical method compared to other transesterification methods.

KEYWORDS: 
Biodiesel; Microwave; Sour cherry kernel oil; Transesterification
RESUMEN

En este estudio, el aceite de semilla de cereza ácida se convirtió en biodiesel mediante transesterificación asistida por microondas. Se realizaron evaluaciones de varias variables, como tiempo de reacción (1, 2, 3, 4 y 5 min), potencia de microondas (100, 200, 300, 400 y 500 W), relación molar metanol/aceite (3, 6, 9, 12 y 15) y concentración de catalizador (KOH) (0,3%, 0,6%, 0,9%, 1,2% y 1,5%). La eficiencia de los ésteres metílicos de ácidos grasos aumentó en respuesta a tiempos de reacción más prolongados, mayor potencia de microondas, mayor relación molar metanol/aceite y mayores concentraciones de catalizador hasta el nivel óptimo. La condición de reacción óptima de la transesterificación asistida por microondas fue una potencia de microondas de 300 W, una concentración de catalizador del 1,2%, una relación molar de metanol/aceite de 12 y un tiempo de reacción de 4 min. La transesterificación asistida por microondas fue más efectiva que los métodos de transesterificación asistida por baño ultrasónico, óhmico, con agitador magnético y con sonda ultrasónica. En conclusión, la transesterificación asistida por microondas puede sugerirse como un método rápido, eficiente y económico en comparación con otros métodos de transesterificación.

PALABRAS CLAVE: 
Aceite de semilla de cereza ácida; Biodiesel; Microonda; Transesterificación

Submitted: 05  April  2023; Accepted: 18  December  2023; Published online: 10  April  2024

Citation/Cómo citar este artículo: Golmakani MT, Niakousari M, Peykar A, Safaeipour T. 2024. Microwave-assisted transesterification of sour cherry kernel oil for biodiesel production: comparison with ultrasonic bath-, ultrasonic probe-, and ohmic-assisted transesterification methods. Grasas y Aceites 75 (1), e545. https://doi.org/10.3989/gya.0429231

CONTENT

1. INTRODUCTION

 

Many sour cherry cultivars have a characteristic tart taste since their acid/sugar ratios are higher in comparison with the sweet cherry cultivars. The strong tartness of sour cherry cultivars limits the fresh consumption of sour cherries (Yilmaz et al., 2019Yilmaz FM, Görgüç A, Karaaslan M, Vardin H, Bilek SE, Uygun Ö, Bircan C. 2019. Sour Cherry By-products: Compositions, Functional Properties and Recovery Potentials. Crit. Rev. Food Sci. Nutr. 59, 3549–3563. https://doi.org/10.1080/10408398.2018.1496901). Thus, most sour cherries are industrially processed and consumed products to make canned or frozen food, jam, and juice. The global sour cherry production in 2019 was about 1.5 million tons (Almasi et al., 2021Almasi S, Najafi G, Ghobadian B, Jalili S. 2021. Biodiesel production from sour cherry kernel oil as novel feedstock using potassium hydroxide catalyst: Optimization using response surface methodology. ISBAB 35, 102089. https://doi.org/10.1016/j.bcab.2021.102089). The largest sour cherry harvests occur in Europe, accounting for 62% of the total worldwide production. Sour cherry by-products consist of pomace and kernel. Sour cherry kernel comprises 7-15% of the whole fruit and consists of two main parts: shell (75-80%) and kernel (20-25%). The sour cherry kernel is made of 7.2% moisture, 4.4% ash, 46.6% carbohydrates, 29.3% protein, and 17-36% oil (Yilmaz et al., 2019Yilmaz FM, Görgüç A, Karaaslan M, Vardin H, Bilek SE, Uygun Ö, Bircan C. 2019. Sour Cherry By-products: Compositions, Functional Properties and Recovery Potentials. Crit. Rev. Food Sci. Nutr. 59, 3549–3563. https://doi.org/10.1080/10408398.2018.1496901). Thus, sour cherry kernel oil (SCKO) is an attractive and valuable source for biodiesel production (Almasi et al., 2021Almasi S, Najafi G, Ghobadian B, Jalili S. 2021. Biodiesel production from sour cherry kernel oil as novel feedstock using potassium hydroxide catalyst: Optimization using response surface methodology. ISBAB 35, 102089. https://doi.org/10.1016/j.bcab.2021.102089).

Biodiesel is an alternative fuel for diesel engines and is made from renewable biological sources such as vegetable oils and animal fats (Zhang et al., 2010Zhang S, Zu Y, Fu Y, Luo M, Zhang D, Efferth T. 2010. Rapid microwave-assisted transesterification of yellow horn oil to biodiesel using a heteropolyacid solid catalyst. Bioresour. Technol. 101, 931–936. http://doi.org/10.1016/j.biortech.2009.08.069). However, since edible oils are more globally needed for food security, non-edible oils would be ideally considered for biodiesel production (Mahlinda et al., 2017Mahlinda S, Supardan MD, Husin H, Riza M, Muslim A. 2017. A comparative study of biodiesel production from screw pine fruit seed: using ultrasound and microwave assistance in in-situ transesterification. JESTEC 12, 3412–3425). Biodiesel is more environmentally friendly than diesel because of its many advantages, such as biodegradability, renewability, low toxicity, secure usability and storage, adaptability to existing engines, and good blending ability with petroleum-based diesel fuels (Zhang et al., 2012Zhang H, Ding J, Zhao Z. 2012. Microwave assisted esterification of acidified oil from waste cooking oil by CERP/PES catalytic membrane for biodiesel production. Bioresour. Technol. 123, 72–77. http://dx.doi.org/10.1016/j.biortech.2012.06.082). The most commonly used method of biodiesel production is the transesterification of vegetable oils and animal fats (Ma and Hanna, 1999Ma F, Hanna MA. 1999. Biodiesel production: a review. Bioresour. Technol. 70, 1–15. https://doi.org/10.1016/S0960-8524(99)00025-5). Biodiesel production processes are based on either conventional or novel heating methods.

The heating method employed in transesterification is a crucial factor in biodiesel production. Conventional heating methods such as magnetic stirrer, hot plate, and water bath require longer reaction times with higher energy inputs that usually render them inefficient (Lin and Chen, 2017Lin J, Chen Y. 2017. Production of biodiesel by transesterification of Jatropha oil with microwave heating. J. Taiwan Inst. Chem. Eng. 75, 43–50. http://dx.doi.org/10.1016/j.jtice.2017.03.034; Dehghan et al., 2019Dehghan L, Golmakani M-T, Hosseini SMH. 2019. Optimization of microwave-assisted accelerated transesterification of inedible olive oil for biodiesel production. Renew. Energ. 138, 915–922. https://doi.org/10.1016/j.renene.2019.02.017). Meanwhile, novel heating methods such as membrane reactors, reactive distillation columns, reactive absorption, ultrasonic, and microwave radiation significantly influence the final conversion, efficiency, and the quality of the product in particular (Talebian-Kiakalaieh et al., 2013Talebian-Kiakalaieh A, Amin NAS, Mazaheri H. 2013. A review on novel processes of biodiesel production from waste cooking oil. Appl. Energy 104, 638–710. http://dx.doi.org/10.1016/j.apenergy.2012.11.061). An alternative heating system is “microwave radiation”, which has recently gained popularity as a method of conducting chemical reactions. When a reaction is carried out under microwaves, the reaction is efficiently accelerated in a short reaction time by the effect of microwaves. This usually results in a drastic reduction in the quantity of by-products and a short separation time (Azcan and Danisman, 2008Azcan N, Danisman A. 2008. Microwave assisted transesterification of rapeseed oil. Fuel 87, 1781–1788. http://doi.org/10.1016/j.fuel.2007.12.004).

The current research aimed at evaluating several variables of the reaction conditions, namely, microwave power, methanol/oil mole ratio, catalyst concentration, and reaction time in the microwave-assisted transesterification (MAT) of SCKO. The MAT of SCKO under optimal condition was compared to the performance of ohmic-, magnetic stirrer-, ultrasonic probe-, and ultrasonic bath-assisted transesterification methods (OAT, MSAT, UPAT, and UBAT, respectively).

2. MATERIALS AND METHODS

 

2.1. Materials

 

Potassium hydroxide, ethanol, hydrochloric acid, sodium sulfate, sodium chloride, TBHQ, sulfuric acid, chloroform, sodium thiosulfate, methanol, acetyl chloride, potassium iodide, methyl laurate, phenolphthalein, hexane, and acetic acid were of analytical grade and were purchased from Sigma-Aldrich (St. Louis, MO) and Merck (Darmstadt, Germany). SCKO was purchased from Mahya Company (Shiraz, Iran).

2.2. Microwave-assisted transesterification (MAT)

 
2.2.1. Experimental procedure
 

The MAT of SCKO was carried out in methanol/oil mole ratios of 3, 6, 9, 12, and 15, along with KOH catalyst concentrations of 0.3, 0.6, 0.9, 1.2, and 1.5%, as well as microwave power values of 100, 200, 300, 400, and 500 W. The reaction time was either 1, 2, 3, 4, or 5 min. All experiments were designed based on changing one variable at a time and keeping the rest of the variables constant at their center point (i.e. microwave power of 300 W, methanol/oil mole ratio of 9, catalyst concentration of 0.9%, and reaction time of 3 min). Effects of each variable on the weight efficiency, purity, and final efficiency of the production of fatty acid methyl esters (FAME) were investigated and the optimal level for each parameter was determined. Eq. (1) was used for determining the amount of oil in each test.

M W o i l   =   3   ×   Ʃ   ( M W i   ×   X i )   +   38  Eq. (1)

Mwoil- Molecular weight of oil

Mwi- Molecular weight of fatty acids in oil

Xi- Mass ratio of fatty acids in oil

A known quantity of catalyst (KOH) was initially dissolved in methanol and the resultant solution was then added to the SCKO. The reaction was carried out in a microwave oven (Samsung, 2450 MHz, model ME3410W), equipped with a condenser. The reaction was captured immediately by immersing the glass reactor in an ice bath. As the reaction was stopped, the product was kept in a separating funnel overnight, when biodiesel was separated from glycerol. The crude FAME remained in the upper phase, while the catalyst and unreacted methanol were situated in the lower glycerol phase, meaning that small amounts of catalyst, methanol, and glycerol were present in the upper phase (Dehghan et al., 2021Dehghan L, Golmakani M-T, Hosseini SMH. 2021. Improving biodiesel yield from pre-esterified inedible olive oil using microwave-assisted transesterification method. Grasas Aceites 72, e417. https://doi.org/10.3989/gya.0336201). Excess methanol in the methyl ester phase was evaporated by a magnetic stirrer equipped with a condenser at 80 ºC for 30 min at 600 rpm (Azcan and Danisman, 2008Azcan N, Danisman A. 2008. Microwave assisted transesterification of rapeseed oil. Fuel 87, 1781–1788. http://doi.org/10.1016/j.fuel.2007.12.004). After separating the biodiesel phase, it was further washed with water to ensure a complete removal of glycerol, catalyst, and other contaminants. Then, a magnetic stirrer at the agitation speed of 400 rpm for 1 h was used to remove the remaining moisture at 60 °C (Alishahi et al., 2021Alishahi A, Golmakani MT, Niakousari M. 2021. Feasibility Study of Microwave-Assisted Biodiesel Production from Vegetable Oil Refinery Waste. Eur. J. Lipid Sci. Technol. 123, 2000377. https://doi.org/10.1002/ejlt.202000377). To determine the purity of the FAME, methyl laurate was used as internal standard. The weight efficiency, purity, and final efficiency of the resultant FAME were determined according to the following equations:

W e i g h t   e f f i c i e n c y   ( % )   =   ( G r o s s   m e t h y l   e s t e r   ( g ) / C o n s u m a b l e   p r i m a r y   o i l   ( g ) )   ×   100  Eq. (2)
P u r i t y   ( % )   =   [ ( A r e a   o f   m e t h y l   e s t e r   p e a k / A r e a   o f   s t a n d a r d   p e a k )   ×   ( S t a n d a r d   w e i g h t / M e t h y l   e s t e r   w e i g h t )   ]   ×   100  Eq. (3)
F i n a l   e f f i c i e n c y   ( % )   =   ( P u r i t y   o f   t h e   m e t h y l   e s t e r   ×   W e i g h t   e f f i c i e n c y   o f   m e t h y l   e s t e r )   /   100  Eq. (4)
2.2.2. Physicochemical properties of FAME
 

The kinematic viscosity, refractive index, and density of biodiesel were measured according to the guidelines of the American Society for Testing Materials (ASTM; D445), the AOCS Cc7-25 Official Method, and the AOCS 1a-64 Official Method, respectively (AOCS, 2000AOCS. 2000. Official Methods and Recommended Practices of the American Oil Chemists’ Society (5th Ed.). USA, AOCS Press, Champaign, Illinois.; ASTM, 2013ASTM. 2013. Standard Specification for Biodiesel Fuel Blend Stock (B100) for Distillate Fuels, ASTM D6751-12.; Golmakani et al., 2022Golmakani M-T, Dehghan L, Rahimizad N. 2022. Biodiesel production enhanced by ultrasound-assisted esterification and transesterification of inedible olive oil. Grasas Aceites 73, e447. https://doi.org/10.3989/gya.1233202). The fatty acid (FA) composition and color attributes of biodiesel were evaluated using a method described by Dehghan et al. (2019)Dehghan L, Golmakani M-T, Hosseini SMH. 2019. Optimization of microwave-assisted accelerated transesterification of inedible olive oil for biodiesel production. Renew. Energ. 138, 915–922. https://doi.org/10.1016/j.renene.2019.02.017.

2.3. Comparison of different transesterification methods

 

The OAT, MSAT, UPAT, and UBAT methods were compared to the optimal conditions of MAT. The weight efficiency, purity, and final efficiency of FAME produced by different transesterification methods were determined according to Eq. (2), Eq. (3), and Eq. (4), respectively.

The reaction conditions in the MSAT, OAT, UPAT, and UBAT methods were similar to those of MAT (300 W power value, methanol/oil mole ratio of 12, reaction time of 4 min, and KOH concentration of 1.2%) unless otherwise stated. In the MSAT method, a magnetic stirrer (Labinco model L81, DG Breda, Netherlands) operated at 600 rpm for 140 min. In the OAT method, an ohmic reactant entered a 50-mL glass balloon and two holes (2 cm in diameter) were made on the sides of the balloon for the entry of electrodes. The applied voltage and salt concentration in this study were 200 V and 0.25%, respectively. In the UPAT method, an ultrasonic probe was used (Bandelin HD 3200, Bandelin Electronics, Berlin, Germany). The substrates were sonicated in a high-grade titanium tip (TT13, 13 mm diameter) with a constant horn depth of 2 cm. In the UBAT method, an ultrasonic bath was used (Bandelin, DT 255H).

2.3.1. Physicochemical properties
 

The kinematic viscosity, refractive index, density, fatty acid composition, and color attributes of the resultant FAME, produced with different transesterification methods, were measured according to section 2.2.2.

2.3.2. Thermal properties of SCKO esters
 

Cloud, flash, fire, and pour points were calculated according to the American Society for Testing Materials (ASTM, 2013ASTM. 2013. Standard Specification for Biodiesel Fuel Blend Stock (B100) for Distillate Fuels, ASTM D6751-12.). Also, a laser thermometer (TM-939, Lutron, Taiwan) was used for measuring the temperature.

2.3.3. Energy consumption
 

The amounts of energy used in each step of the reactions per transesterification method, separation of methanol, washing, and drying were monitored using a digital electric energy meter (a watt-hour meter) at the entrance of the electrical power supply. The amount of energy (power consumption (W)) was determined and then multiplied by time to get the total energy consumption (Wh) (Eq. (5)) (Motasemi and Ani, 2012Motasemi F, Ani FN. 2012. A review on microwave-assisted production of biodiesel. Renewable Sustainable Energy Rev. 16, 4719–4733. https://doi.org/10.1016/j.rser.2012.03.069). The energy consumed in all stages was added together and by applying Eq. (6), the amount of energy consumed to produce 1 g of FAME was calculated as the relative energy consumption.

T o t a l   e n e r g y   c o n s u m p t i o n   ( W h )   =   P o w e r   c o n s u m p t i o n   ( W )   ×   T i m e   ( h )  Eq. (5)
R e l a t i v e   e n e r g y   c o n s u m p t i o n   ( W h / g )   =   T o t a l   e n e r g y   c o n s u m p t i o n   ( W h )   /   F i n a l   m e t h y l   e s t e r   w e i g h t   ( g )  Eq. (6)

For producing 1 kWh of energy, 800 g of CO2 entered the environment. CO2 production and relative CO2 production were measured according to the following equations:

C O 2   p r o d u c t i o n   ( g )   =   E n e r g y   c o n s u m p t i o n   ( W h )   ×   0.8   ( g / W h )  Eq. (7)
R e l a t i v e   C O 2   p r o d u c t i o n   =   C O 2   p r o d u c t i o n   ( g )   /   F i n a l   m e t h y l   e s t e r   w e i g h t   ( g )  Eq. (8)

2.4. Statistical analysis

 

All experiments were done in three repetitions. Their mean values and standard deviations were calculated. The mean comparison was made to determine the differences among the mean values via SAS software (Statistical Analysis Software, version 9.1; SAS Institute Inc. Cary, NC).

3. RESULTS AND DISCUSSION

 

The physicochemical properties of SCKO are shown in Table 1. The amount of free fatty acid (FFA) for alkaline transesterification should be less than 5% and the moisture content should be less than 0.5% (Cavalcante et al., 2010Cavalcante KS, Penha MN, Mendonca KK, Louzeiro HC, Vasconcelos AC, Maciel AP, Souza AG, Silva FC. 2010. Optimization of transesterification of castor oil with ethanol using a central composite rotatable design (CCRD). Fuel 89, 1172–1176. https://doi.org/10.1016/j.fuel.2009.10.029). According to the preliminary experiments, SCKO showed the necessary characteristics to participate in the transesterification reaction. Oleic acid (C18:1) and linoleic acid (C18:2) were the main unsaturated fatty acids in SCKO. Our findings are consistent with the results of Popa et al. (2011)Popa V, Misca C, Bordean D, Raba D, Stef D, Dumbrava D. 2011. Characterization of sour cherries (Prunus cerasus) kernel oil cultivars from Banat. J. Agroaliment. Processes Technol. 15, 398–401., Gornas et al. (2016)Gornas P, Rudzinska M, Raczyk M, Misina I, Soliven A, Seglina D. 2016. Composition of bioactive compounds in kernel oils recovered from sour cherry (Prunus cerasus L.) by-products: Impact of the cultivar on potential applications. Ind. Crops Prod. 82, 44–50. https://doi.org/10.1016/j.indcrop.2015.12.010 and Korlesky et al. (2016)Korlesky NM, Stolp LJ, Kodali DR, Goldschmidt R, Byrdwell WC. 2016. Extraction and characterization of montmorency sour cherry (Prunus cerasus L.) pit oil. J. Am. Oil Chem.’ Soc. 93, 995–1005. http://doi.org/10.1007/s11746-016-2835-4 regarding the properties of SCKO.

TABLE 1.  Physicochemical properties of pre-esterified inedible sour cherry kernel oil.
Physicochemical property value
Free fatty acids (%, as oleic acid) 3.5
Refractive index 1.479
Saponification value (mg KOH/g) 163.812
Acid value (mg KOH/g) 6.965
Density (kg/m3) 869.6
Moisture and volatile matters (%) 0.34
Viscosity at 40 C (mm2/s) 28.16
Equivalent saponification value 1027.39
Color attribute
L* 89.33
a* -2.00
b* 35.33
Fatty acid composition (%)
Myristic acid 0.67
Palmitic acid 10.59
Palmitoleic acid 0.63
Stearic acid 1.43
Oleic acid 40.43
Linoleic acid 44.14
α-Linolenic acid 1.05
Eleostearic acid 0.71
Arachidic acid 0.33
Saturated fatty acid (SFA) 13.02
Unsaturated fatty acid (UFA) 86.98
Polyunsaturated fatty acid (PUFA) 45.90

3.1. Effects of influential parameters on biodiesel efficiency of MAT

 
3.1.1. Reaction time
 

Figure 1a shows variations in weight efficiency, purity, and final efficiency with respect to the reaction time. Within the first 4 min, the weight efficiency, purity, and final efficiency increased with the extension of the transesterification time. After 4 min (microwave power of 300 W, methanol/oil mole ratio of 9, and catalyst concentration of 0.9%), the weight efficiency, purity, and final efficiency decreased. Thus, 4 min was considered as an optimal reaction time. At the beginning of the process, due to the non-uniform distribution of methanol in the oil, the reaction was slow. However, the reaction rate increased with time. This means that in the initial stages, while the reactants had the least contact with the microwaves, FAME production was low in purity and efficiency (Sajjadi et al., 2014Sajjadi B, Abdul Aziz AR, Ibrahim S. 2014. Investigation, modelling and reviewing the effective parameters in microwave-assisted transesterification. Renewable Sustainable Energy Rev. 37, 762–777. https://doi.org/10.1016/j.rser.2014.05.021). Prolonging the reaction time above the optimal one led to a decrease in weight efficiency, purity, and final efficiency from several angles. Over time, the reversibility of the transesterification reaction caused an increase in the solubility of glycerol and the reaction slightly changed in the reverse direction, thereby resulting in by-products and reducing the production of FAME. Also, the long reaction time caused the reactants to overheat. Methanol evaporated from the reaction medium after reaching the boiling point and reduced the efficiency of FAME production. In addition, by increasing the reaction time, the costs related to the amount of energy required to carry out the reaction will also increase (Chen et al., 2012Chen K, Lin Y, Hsu K, Wang H. 2012. Improving biodiesel yields from waste cooking oil by using sodium methoxide and a microwave heating system. Energy 38, 151156. https://doi.org/10.1016/j.energy.2011.12.020; Leung et al., 2010Leung DYC, Wu X, Leung MKH. 2010. A review on biodiesel production using catalyzed transesterification. Appl. Energy 87, 1083–1095. https://doi.org/10.1016/j.apenergy.2009.10.006; Patil et al., 2011Patil PD, Gude VG, Mannarswamy A, Cooke P, Munson-McGee S, Nirmalakhandan N, Lammers P, Deng S. 2011. Optimization of microwave-assisted transesterification of dry algal biomass using response surface methodology. Bioresour. Technol. 102, 1399–1405. https://doi.org/10.1016/j.biortech.2010.09.046). Similarly, Azkan and Yilmaz (2013)Azcan N, Yilmaz O. 2013. Microwave assisted transesterification of waste frying oil and concentrate methyl ester content of biodiesel by molecular distillation. Fuel 104, 614–619. https://doi.org/10.1016/j.fuel.2012.06.084 reported the effects of reaction time on the final efficiency of FAME production from waste from frying oil.

medium/medium-GYA-75-01-e545-gf1.png
FIGURE 1.  Effects of (a) reaction time, (b) microwave power, (c) methanol/oil mole ratio, and (d) catalyst concentration on microwave-assisted transesterification of sour cherry kernel oil; Mean ± SD (n = 3); Statistical test: ANOVA and multiple comparison of means using Duncan’s multiple range test; (P < 0.05); Each factor was optimized by considering an intermediate value (center point) of other factors (i.e., microwave power of 300 W, methanol/oil mole ratio of 9, catalyst concentration of 0.9%, and reaction time of 3 min).
3.1.2. Microwave power
 

Figure 1b shows variations in weight efficiency, purity, and final efficiency with respect to microwave power. The weight efficiency, purity, and final efficiency increased in response to the increase in microwave power up to 300 W (reaction time of 3 min, methanol/oil mole ratio of 9, and catalyst concentration of 0.9%). Maximum weight efficiency, purity, and final efficiency reached 97.14, 75.26, and 73.11%, respectively, when biodiesel production from the SCKO operated at 300 W. This can be justified by the fact that the increase in microwave power accelerated the electromagnetic wave transfer through the molecular components of the mixture and their energy spread at a higher rate within the reactant mixture. Thus, the final efficiency increased. However, by increasing the microwave power to above 300 W, the reactant mixture and the structure of organic compounds became susceptible to damage. Triglycerides broke down and were converted to FFA. An excessive increase in power rendered an intense and chaotic interaction between molecules, thereby reducing the formation rate of the final, intended product. Similarly, Zu et al. (2009Zu Y, Zhang S, Fu Y, Liu W, Liu Z, Luo M, Efferth T. 2009. Rapid microwave-assisted transesterification for the preparation of fatty acid methyl esters from the oil of yellow horn (Xanthoceras sorbifolia Bunge.). Eur. Food Res. Technol. 229, 43–49. https://doi.org/10.1007/s00217-009-1024-1) produced biodiesel using yellow horn (Xanthoceras sorbifolia Bunge.) oil and reported that at irradiation power of 500 W the highest efficiency was achieved in 6 min. However, when the power of 700 W was applied, the conversion efficiency of FAME began declining, because different raw materials have different appropriate irradiation power.

3.1.3. Methanol/oil mole ratio
 

Figure 1c shows the variations in weight efficiency, purity, and final efficiency with respect to the methanol/oil mole ratio. The weight efficiency, purity, and final efficiency increased in response to the increase in methanol/oil mole ratio from 3 to 12 (reaction time of 3 min, microwave power of 300 W, and catalyst concentration of 0.9%). However, the weight efficiency, purity, and final efficiency decreased when the methanol/oil mole ratio increased from 12 to 15. Thus, the methanol/oil mole ratio of 12 was considered optimal. The highest weight efficiency, purity, and final efficiency of FAME (98.90, 80.52, and 79.63%, respectively) were obtained at the mole ratio of 12. An excessive increase in methanol in several aspects reduced its production efficiency to esterify the triglycerides to FAME. Since methanol is highly capable of absorbing microwaves, increasing its ratio causes a higher absorption of waves when sufficient amounts of methanol exist. The temperature of the reaction mixture increased with less intensity (Lin et al., 2014Lin Y, Hsu K, Lin J. 2014. Rapid palm-biodiesel production assisted by a microwave system and sodium methoxide catalyst. Fuel 115, 306–311. https://doi.org/10.1016/j.fuel.2013.07.022), while excess methanol made catalyst separation difficult at the end of the reaction. Increasing the methanol/oil mole ratio beyond a certain value increased the glycerol solubility and led to foam formation, thereby lowering the efficiency (Sharma et al., 2019Sharma A, Kodgire P, Kachhwaha SS. 2019. Biodiesel production from waste cotton-seed cooking oil using microwave-assisted transesterification: Optimization and kinetic modeling. Renewable Sustainable Energy Rev. 116, 109394. https://doi.org/10.1016/j.rser.2019.109394). In addition, an excess of glycerol drove the shifted equilibrium towards the reactants, and, thus, lowered the efficiency of biodiesel conversion when glycerol remained in the solution (Mahlinda et al., 2017Mahlinda S, Supardan MD, Husin H, Riza M, Muslim A. 2017. A comparative study of biodiesel production from screw pine fruit seed: using ultrasound and microwave assistance in in-situ transesterification. JESTEC 12, 3412–3425). In a similar study, Zhang et al. (2010)Zhang S, Zu Y, Fu Y, Luo M, Zhang D, Efferth T. 2010. Rapid microwave-assisted transesterification of yellow horn oil to biodiesel using a heteropolyacid solid catalyst. Bioresour. Technol. 101, 931–936. http://doi.org/10.1016/j.biortech.2009.08.069 produced biodiesel using yellow horn oil and reported that the transesterification could be accelerated by increasing the amounts of methanol. The high mole ratio of methanol to oil could enhance the conversion efficiency of FAME. On the other hand, excessive methanol amounts reduced the concentrations of catalyst and reactant, which retarded the reaction and aggravated the recovery of the solvents.

3.1.4. Catalyst concentration
 

Figure 1d shows variations in weight efficiency, purity, and final efficiency with respect to catalyst concentration. Weight efficiency, purity, and final efficiency increased when the amount of catalyst concentration increased from 0.3 to 1.2% (reaction time of 3 min, microwave power of 300 W, and methanol/oil mole ratio of 9). A higher catalyst concentration caused proper physical contact between the reactants that led to an increase in purity and final efficiency. Since increasing the catalyst concentration from 1.2 to 1.5% had no considerable impact on the efficiency and purity of FAME, the catalyst concentration of 1.2% was considered optimal. High amounts of alkaline catalyst increased the possibility of soap formation, which caused an emulsion to form between soap and water molecules. This emulsion entraps FAME and makes their separation difficult, so that some of them remain unrecovered (Atapour and Kariminia, 2011Atapour M, Kariminia H. 2011. Characterization and transesterification of Iranian bitter almond oil for biodiesel production. Appl. Energy 88, 2377–2381. https://doi.org/10.1016/j.apenergy.2011.01.014). An excessive increase in the catalyst concentration increased the kinematic viscosity of the mixture, created a gel, and led to problems in separating the glycerol phase (Sajjadi et al., 2014Sajjadi B, Abdul Aziz AR, Ibrahim S. 2014. Investigation, modelling and reviewing the effective parameters in microwave-assisted transesterification. Renewable Sustainable Energy Rev. 37, 762–777. https://doi.org/10.1016/j.rser.2014.05.021). In a similar study, Sharma et al. (2019)Sharma A, Kodgire P, Kachhwaha SS. 2019. Biodiesel production from waste cotton-seed cooking oil using microwave-assisted transesterification: Optimization and kinetic modeling. Renewable Sustainable Energy Rev. 116, 109394. https://doi.org/10.1016/j.rser.2019.109394 produced biodiesel using waste cotton-seed cooking oil, and reported that the excessive amount of heterogeneous catalyst increased washing time and decreased the formation of biodiesel as the reactant mixture became more viscous and thus, increased resistance to mass transfer. A suitable amount of catalyst reduces catalyst waste and avoids pollution in bodies of water.

3.2. Investigation of the FAME produced by MAT

 
3.2.1. Fatty acid composition
 

Table 2 shows variations in the fatty acid composition of SCKO FAME with respect to different MAT variables. It seems that different microwave conditions had no significant effect on the transesterification of different fatty acids in terms of chain length and saturation degree. Thus, strong similarities existed between the percentages of fatty acids in the FAME produced under different MAT conditions.

TABLE 2.  Effect of reaction time, microwave power, methanol/oil mole ratio, and catalyst concentration o nfatty acid composition (%) of sour cherry kernel oil methyl esters.
Transesterification variable Fatty acids
Myristic acid Palmitic acid Palmitoleic acid Stearic acid Oleic acid Linoleic acid α-Linolenic acid Eleostearic acid Arachidic acid
Reaction time (min)
1 0.35±0.31* 8.88±0.44 0.53±0.03 0.61±0.03 41.95±2.10 46.05±2.30 0.48±0.02 0.79±0.04 0.36±0.02
2 0.51±0.03 9.25±0.46 0.70±0.04 1.50±0.08 39.83±1.99 46.80±2.34 0.39±0.02 0.70±0.04 0.32±0.02
3 1.33±0.07 9.63±0.48 0.71±0.04 1.24±0.06 39.85±1.98 45.71±2.29 0.61±0.03 0.66±0.03 0.27±0.01
4 0.26±0.01 7.51±0.38 0.42±0.02 1.33±0.05 42.76±2.14 46.70±2.39 0.21±0.01 0.48±0.02 0.33±0.02
5 0.18±0.1 8.86±0.44 0.64±0.03 1.50±0.07 41.87±2.09 45.46±2.26 0.50±0.02 0.67±0.03 0.32±0.02
Microwave power (W)
100 0.28±0.01 9.02±0.45 0.63±0.02 1.90±0.09 39.58±1.98 47.31±2.37 0.70±0.04 0.43±0.02 0.15±0.01
200 1.09±0.05 10.18±0.51 0.57±0.03 1.62±0.08 38.21±1.91 45.47±2.27 0.67±0.03 1.69±0.08 0.29±0.01
300 1.14±0.06 9.07±0.45 0.68±0.03 1.42±0.07 38.84±1.94 46.78±2.34 0.55±0.03 0.35±0.02 1.17±0.06
400 1.24±0.06 6.84±0.34 0.90±0.00 1.94±0.10 38.04±1.89 46.24±2.31 0.32±0.02 1.93±0.10 2.55±0.13
500 0.77±0.04 8.87±0.44 0.57±0.03 1.75±0.09 40.18±2.01 45.43±2.27 0.57±0.03 1.15±0.06 0.71±0.04
Mole ratio (methanol/oil)
3 0.80±0.00 9.05±0.44 0.48±0.02 1.19±0.06 40.03±2.00 46.48±2.32 0.39±0.02 1.58±0.07 0.45±0.02
6 0.59±0.03 10.17±0.51 1.46±0.07 1.49±0.07 38.83±1.93 44.87±2.23 0.98±0.05 1.05±0.05 0.67±0.03
9 0.82±0.04 9.87±0.49 1.11±0.06 1.36±0.07 38.06±1.88 45.33±2.26 0.70±0.03 1.97±0.10 0.79±0.03
12 0.71±0.04 9.04±0.45 0.56±0.03 1.87±0.09 40.86±2.04 44.68±2.22 0.48±0.02 1.36±0.06 0.44±0.02
15 1.79±0.09 8.63±0.43 0.59±0.03 1.55±0.07 39.50±1.98 45.68±2.27 0.67±0.03 1.12±0.05 0.47±0.02
Catalyst concentration (%)
0.3 1.24±0.06 8.97±0.43 0.45±0.02 1.49±0.07 39.91±1.97 44.47±2.20 1.04±0.05 1.24±0.06 1.19±0.06
0.6 1.03±0.05 9.08±0.45 0.61±0.03 1.47±0.07 39.12±1.92 46.3±2.32 0.84±0.13 0.50±0.00 1.05±0.04
0.9 1.63±0.08 7.46±0.37 0.30±0.02 0.27±0.01 40.07±1.98 46.12±2.30 1.45±0.07 1.06±0.05 1.65±0.08
1.2 1.01±0.04 9.61±0.47 0.47±0.02 1.04±0.05 39.33±1.94 45.87±2.28 0.25±0.01 0.95±0.04 1.48±0.06
1.5 0.71±0.04 9.07±0.45 0.57±0.03 0.28±0.01 39.83±1.99 46.78±2.34 1.42±0.02 1.05±0.05 0.29±0.01

* Mean ± SD (n = 3); Statistical test: ANOVA and multiple comparison of means using Duncan’s multiple range test; Constant condition: Microwave power of 300 W, reaction time of 3 min, catalyst concentration of 0.9%, and methanol/oil mole ratio of 9.

3.2.2. Physical properties
 

Table 3 shows variations in the physical properties of SCKO FAME with respect to different MAT variables. The kinematic viscosity of SCKO was measured as 28.16 mm2/s in this study. The kinematic viscosity of the final FAME should be 1.9-6.0 centistokes (mm2/s), according to the ASTM 6751 (American Standard) and should be 3.5-5.0 centistokes (mm2/s), according to the EN 14214 (European standard) (Kantikar et al., 2011Kanitkar A, Balasubramanian S, Lima M, Boldor D. 2011. A critical comparison of methyl and ethyl esters production from soybean and rice bran oil in the presence of microwaves. Bioresour. Technol. 102, 7896–7902. http://doi.org/10.1016/j.biortech.2011.05.091). As can be seen, there were significant differences among the viscosities of FAME produced at different microwave reaction times. Samples exposed to 1- and 2-min reaction times were more than 6.0 mm2/s and were outside the aforementioned limits. In contrast, other reaction times were within the permissible range of the defined standards. The best result (i.e. the lowest kinematic viscosity of 3.78 mm2/s) was obtained after 4 min of reaction time. By increasing the reaction time and increasing the purity of the produced FAME (i.e. decreasing the molecular weight), the process of kinematic viscosity changes declined and reached the lowest value after 4 min, but with a further increase in the reaction time and due to the purity reduction and an increase in the molecular weight, the kinematic viscosity increased. There was a negative correlation between kinematic viscosity and final efficiency (kinematic viscosity = (-0.069 × final efficiency) + 9.11, R2 = 0.93 for reaction time; kinematic viscosity = (-0.086 × final efficiency) + 9.90, R2 = 0.90 for microwave power; kinematic viscosity = (-0.11 × final efficiency) + 11.72, R2 = 0.91 for mole ratio; kinematic viscosity = (-0.43 × final efficiency) + 30.30, R2 = 0.98 for catalyst concentration).

TABLE 3.  Effects of microwave-assisted transesterification on physical properties of sour cherry kernel oil fatty acid methyl esters.
Transesterification variable Viscosity (mm2/s) Refractive index Density (kg/m3) Color attribute
L* a* b*
Time (min)
1 6.43±0.32a* 1.487±0.073a 878.43±43.92c 82.00±4.36b -4.00±1.00b 48.67±0.58a
2 6.05±0.30b 1.486±0.073a 880.28±44.01c 81.33±3.06b -5.00±1.00c 48.00±1.00a
3 4.37±0.22c 1.461±0.073b 884.13±44.21b 82.00±3.00b -3.00±1.00b 46.00±1.00b
4 3.78±0.19e 1.468±0.073b 900.01±45.00a 89.67±1.53a -3.67±0.58b 34.67±2.52c
5 3.97±0.20d 1.459±0.073b 899.68±44.98a 88.67±8.02a -2.33±1.53a 46.33±1.15b
Power (W)
100 6.20±0.30a 1.486±0.073a 880.16±44.00e 84.33±3.51b -2.33±0.58b 44.67±1.53a
200 4.10±0.20c 1.471±0.073c 885.93±44.29c 83.33±7.37b -2.00±0.00b 43.33±3.79a
300 4.00±0.20c 1.469±0.073e 889.70±44.98a 90.67±4.51a -1.67±0.57a 34.67±6.35d
400 4.00±0.20c 1.460±0.073d 887.19±44.35b 87.67±10.02a -2.33±0.58b 37.33±11.02c
500 5.10±0.30b 1.472±0.073b 883.47±44.17d 87.67±4.93a -2.67±1.53c 38.33±3.51b
Mole ratio (Methanol/oil)
3 5.70±0.28a 1.483±0.073a 882.07±44.10d 87.00±07.94a -3.00±1.00b 48.67±0.58a
6 5.70±0.28a 1.483±0.073a 882.11±44.10d 87.67±4.93a -2.33±0.58a 48.00±1.00a
9 4.10±0.20b 1.471±0.073b 886.19±44.30c 89.00±1.00a -2.00±0.00a 46.00±1.00b
12 3.80±0.19d 1.469±0.073c 899.98±44.99a 90.33±2.08a -1.67±0.58a 42.00±4.00c
15 4.00±0.20c 1.460±0.073c 887.12±44.35b 85.67±3.06a -3.00±1.00b 46.33±1.15b
Catalyst concentration (%)
0.3 26.40±1.32a 1.486±0.074a 872.90±43.64d 87.33±2.08a -3.33±0.58d 37.67±3.06b
0.6 26.10±1.30a 1.481±0.074a 873.45±43.67d 82.00±1.00b -2.67±0.58c 35.33±5.13c
0.9 6.01±0.30b 1.473±0.073b 881.98±44.09c 88.67±2.52a -2.67±0.58c 40.00±3.00a
1.2 4.46±0.22c 1.462±0.073c 883.99±44.19b 89.67±3.51a -2.00±1.00b 35.33±7.77c
1.5 4.05±0.20d 1.460±0.073d 886.24±44.31a 90.00±3.00a -1.33±0.58a 35.00±3.61c

* Mean ± SD (n = 3); Statistical test: ANOVA and multiple comparison of means using Duncan’s multiple range test; In each column and for each variable, means with different lowercase letters are significantly different (P < 0.05); Each factor was optimized by considering an intermediate value (center point) of other factors (microwave power of 300 W, methanol/oil mole ratio of 9, catalyst concentration of 0.9%, and reaction time of 3 min).

The density of SCKO was 869.6 kg/m3 and increased after transesterification (Table 3). According to the EN standard, the density of FAME at 15 °C should be in the range of 860-900 kg/m3. All FAME were within the permitted range of the EN standard. The unsaturation degree had no significant effect on the transesterification reaction of the produced FAME. However, due to the conversion of primary triglycerides to FAME, the molecular weight of the final product decreased, whereas the density increased compared to the primary SCKO. There was a significant positive correlation between the density and the final efficiency (density = (0.59 × final efficiency) + 853.16, R2 = 0.91 for reaction time; density = (0.62 × final efficiency) + 849.66, R2 = 0.90 for microwave power; density = (0.68 × final efficiency) + 844.67, R2 = 0.94 for mole ratio; density = (0.22 × final efficiency) + 870.82, R2 = 0.98 for catalyst concentration). Therefore, the highest density of 900.01 kg/m3 was obtained after 4 min microwave power of 300 W, which is consistent with the results of Talebian-Kiakalaieh et al. (2013)Talebian-Kiakalaieh A, Amin NAS, Mazaheri H. 2013. A review on novel processes of biodiesel production from waste cooking oil. Appl. Energy 104, 638–710. http://dx.doi.org/10.1016/j.apenergy.2012.11.061 regarding the FAME density of several types of vegetable oils.

The refractive index of SCKO was 1.479 and decreased after transesterification (Table 3). The lowest refractive index (1.460) was acquired and a strong negative correlation existed between the refractive index and the final efficiency (refractive index = (-0.0002 × final efficiency) + 1.4725, R2 = 0.90 for reaction time; refractive index = (-0.0002 × final efficiency) + 1.4774, R2 = 0.90 for microwave power; refractive index = (-0.0002 × final efficiency) + 1.14, R2 = 0.90 for mole ratio; refractive index = (-0.0002 × final efficiency) + 1.47, R2 = 0.94 for catalyst concentration). The obtained results are consistent with the research of Azcan and Yilmaz (2013)Azcan N, Yilmaz O. 2013. Microwave assisted transesterification of waste frying oil and concentrate methyl ester content of biodiesel by molecular distillation. Fuel 104, 614–619. https://doi.org/10.1016/j.fuel.2012.06.084 They reported the refractive index of waste frying oil to be 1.4710 and the resulting FAME to be 1.4575.

The highest purity and efficiency of FAME production were reflected in L* (89.67), a* (-3.67), and b* (34.67) values (Table 3). Initially, increasing the microwave power decreased the a* value (an increase in greenness or a decrease in redness) and b* values (a decrease in yellowness), but after the optimal point, both a * and b * values increased.

3.3. Comparison of different transesterification methods

 

By comparing the mixture of FAME produced by the MSAT, MAT, OAT, UPAT, and UBAT methods, the MAT method showed the highest weight efficiency, purity, and final efficiency, compared to the other transesterification methods. Then, OAT, UPAT, and UBAT showed the highest weight efficiency, purity, and final efficiency, respectively. Weight efficiency, purity, and final efficiency of the MSAT method were the lowest in comparison with other transesterification methods.

3.3.1. Weight efficiency, purity, final efficiency, and fatty acid composition
 

The highest weight efficiency, purity, and final efficiency of FAME production from SCKO were 99.03, 82.21, and 81.41, respectively, using MAT at an operating power of 300 W, methanol/oil mole ratio of 12, catalyst concentration of 1.2%, and reaction time of 4 min (Figure 2a).

medium/medium-GYA-75-01-e545-gf2.png
FIGURE 2.  Effects of different transesterification methods on (a) weight efficiency, (b) purity, and (c) final efficiency of sour cherry kernel oil fatty acid methyl esters; Mean ± SD (n = 3); Statistical test: ANOVA and multiple comparison of means using Duncan’s multiple range test; (P < 0.05); Constant condition: methanol/oil mole ratio of 12 and catalyst concentration of 1.2%; microwave power of 300 W, ohmic voltage of 200 V, salt concentration of 0.25%, and ultrasonic probe power of 150 W.

The purities of FAME produced by different transesterification methods are shown in Figure 2b. It can be clearly seen that the highest purity was obtained after 4, 10, 40, and 120 min of MAT (86.47%), OAT (70.30%), UBAT (57.72%), and MSAT (60.16%) methods, respectively.

Figure 2c compares the efficiency of different transesterification methods. The process of changes in the efficiency correlated significantly with changes in purity. The highest efficiencies of different transesterification methods were 85.52% after 4 min MAT, 69.60% after 4 min OAT, 62.38% after 10 min UPAT, 57.88% after 40 min UBAT, and 54.79% after 120 min MSAT. The highest efficiency in the MSAT method was obtained after 120 min (54.79%), but prolonging the duration further than 120 min caused a decrease in both purity and efficiency.

Table 4 shows variations in the fatty acid composition of SCKO FAME with respect to MAT, OAT, UPAT, UBAT, and MSAT methods. As can be seen, the FA composition of samples produced with different transesterification methods were similar. The transesterification method had no selective effect on the FA in terms of chain length or degree of saturation.

TABLE 4.  Fatty acid methyl ester composition (%) of sour cherry kernel oil produced by different transesterification methods.
Method Reaction time (min) Fatty acid
Myristic acid Palmitic acid Palmitoleic acid Stearic acid Oleic acid Linoleic acid α-Linolenic acid Eleostearic acid Arachidic acid
Microwave
4 0.66±0.67* 10.45±3.92 0.85±0.81 0.75±0.76 39.92±3.13 44.73±6.41 1.48±1.62 0.75±0.21 0.40±0.22
10 0.63±0.03 9.56±0.48 0.57±0.03 0.07±0.00 41.02±2.05 46.01±2.30 1.12±0.06 0.76±0.04 0.26±0.01
40 2.10±0.11 9.21±0.46 2.70±0.13 0.74±0.03 39.92±1.99 43.05±2.12 1.11±0.05 0.30±0.02 0.87±0.04
Ohmic
4 0.99±0.04 7.27±0.31 0.39±0.08 2.06±0.09 39.00±1.89 49.06±2.43 0.73±0.12 0.13±0.03 0.35±0.03
10 1.51±0.57 7.35±0.42 0.44±0.06 2.07±0.12 38.74±2.17 46.79±2.19 0.87±0.12 0.81±1.05 1.42±1.18
40 1.60±0.66 7.64±0.52 0.42±0.06 2.02±0.39 38.76±2.07 46.77±2.21 0.86±0.20 0.88±1.21 1.05±1.10
Ultrasonic probe
4 1.96±0.10 7.66±0.38 0.51±0.03 2.04±0.10 37.77±1.89 46.42±2.32 0.82±0.04 0.13±0.01 2.70±0.13
10 1.44±0.07 6.94±0.35 0.42±0.02 1.98±0.10 37.69±1.88 46.36±2.32 0.93±0.05 1.86±0.09 2.37±0.12
40 2.82±0.14 8.48±0.37 0.45±0.02 2.28±0.11 37.34±1.87 44.36±2.21 1.19±0.06 3.06±0.15 1.02±0.00
Ultrasonic bath
4 1.34±0.07 8.07±0.40 0.45±0.02 1.26±0.06 39.16±1.96 48.68±2.43 0.55±0.03 0.12±0.01 0.38±0.02
10 1.01±0.05 8.06±0.40 0.34±0.02 2.36±0.12 40.05±2.00 46.85±2.34 0.84±0.04 0.03±0.00 0.46±0.02
40 1.01±0.05 8.05±0.40 0.34±0.02 2.35±0.12 40.00±2.00 46.79±2.34 0.97±0.05 0.03±0.00 0.46±0.02
Magnetic stirrer
4 0.60±0.36 8.50±0.41 0.23±0.01 1.51±0.67 41.51±2.12 45.16±2.40 0.68±0.26 0.92±0.92 0.89±0.40
10 1.19±0.05 9.31±0.47 0.88±0.04 1.58±0.07 38.56±1.93 45.70±2.29 0.63±0.03 1.05±0.05 1.09±0.05
40 0.37±0.02 9.52±0.48 0.21±0.01 0.48±0.02 39.14±1.96 48.35±2.42 0.97±0.05 0.67±0.03 0.30±0.01
120 1.20±0.06 7.21±0.36 0.07±0.00 2.09±0.10 39.39±1.97 48.78±2.44 0.75±0.04 0.25±0.01 0.35±0.02
140 0.42±0.02 9.80±0.49 0.40±0.02 0.53±0.03 39.79±1.99 47.66±2.37 0.65±0.03 0.49±0.02 0.25±0.01

* Mean ± SD (n = 3); Statistical test: ANOVA and multiple comparison of means using Duncan’s multiple range test; Constant condition: Microwave power of 300 W, methanol/oil mole ratio of 12, catalyst concentration of 1.2%, ohmic voltage of 200 V, salt concentration of 0.25%, and ultrasonic probe power of 150 W.

3.3.2. Physicochemical properties
 

Viscosity.Table 5 shows variations in the physicochemical properties of the produced FAME with respect to different transesterification methods. Except for the samples produced with the MSAT method, the properties of other transesterification methods were within the permissible limits of ASTM and EN standards. Since the highest purity and weight efficiency of triglycerides to lower molecular weight FAME were observed in the MAT method, the lowest kinematic viscosity was also obtained in this method. Among other transesterification methods, OAT, UPAT, and UBAT showed lower kinematic viscosity values than that of the MSAT method.

TABLE 5.  Effects of different transesterification methods on physical properties of sour cherry kernel oil fatty acid methyl esters.
Method Time (min) Density (kg/m3) Viscosity (mm2/s) Refractive index Color attribute
L* a* b*
Microwave
4 899.90±45.00a* 3.74±0.19b 1.457±0.073b 87.00±6.56a 2.00±0.00a 37.00±6.56b
10 887.49±44.37a 4.02±0.20a 1.460±0.073b 86.33±3.79a 3.33±1.15b 39.67±1.53a
40 874.53±43.73a 4.03±0.20a 1.468±0.073a 83.67±2.08a 3.33±1.15b 42.33±3.79a
Ohmic
4 892.99±37.12a 4.08±0.30a 1.460±0.060a 86.67±6.66b 3.33±0.58a 35.00±2.65a
10 889.15±44.46a 4.03±0.20a 1.460±0.073a 89.00±2.00a 3.33±0.58a 34.00±3.00a
40 883.97±44.20b 4.65±0.23a 1.462±0.073a 87.00±2.00a 4.00±1.00a 32.67±4.04b
Ultrasonic probe
4 884.02±36.09a 4.44±0.25a 1.461±0.060a 89.33±3.06a 3.00±0.00a 34.67±1.53a
10 884.16±44.21a 4.34±0.22a 1.461±0.073a 91.00±2.00a 3.33±0.58a 33.33±0.58a
40 883.75±44.19a 4.83±0.24a 1.462±0.073a 88.00±1.73a 3.67±0.58a 35.00±0.00a
Ultrasonic bath
4 883.09±36.06a 4.43±0.46a 1.463±0.060a 84.00±6.08a 2.00±1.73a 41.67±3.21a
10 883.92±44.20a 4.78±0.24a 1.462±0.073a 86.33±6.11a 3.33±1.15b 40.33±5.69a
40 883.91±44.20a 4.73±0.24a 1.462±0.073a 88.33±3.06a 2.67±0.58a 39.67±2.31a
Magnetic stirrer
4 871.16±35.59b 23.90±7.76a 1.474±0.060a 89.67±6.66a -3.33±0.58c 35.00±2.65a
10 871.12±43.56b 26.37±1.32b 1.473±0.074a 89.00±2.00a -3.33±0.58c 34.00±3.00a
40 875.11±43.76a 6.51±0.33c 1.468±0.073b 87.00±2.00a -4.00±1.00b 32.67±4.04b
120 882.15±44.11a 5.59±0.28d 1.468±0.073b 86.67±2.52a -5.00±1.00a 31.00±2.65b
140 878.45±43.92a 6.40±0.32d 1.467±0.073b 91.67±1.15a -3.00±1.00c 35.67±2.08a

* Mean ± SD (n = 3); Statistical test: ANOVA and multiple comparison of means using Duncan’s multiple range test; In each column and for each method, means with different lowercase letters are significantly different (P < 0.05). Constant condition: methanol/oil mole ratio of 12 and catalyst concentration of 1.2%; microwave power of 300 W, ohmic voltage of 200 V, salt concentration of 0.25%, and ultrasonic probe power of 150 W.

Density. The density is influenced by the weight efficiency of triglycerides to FAME and increases by increasing the purity and decreasing the molecular weight. The MAT method showed the highest density (Table 5). There were no significant differences among the density of FAME produced by OAT, UPAT, and UBAT methods in their optimal conditions. The lowest density occurred as a result of the MSAT method. In addition, the densities of FAME that were produced using all transesterification methods were within the allowed range of the EN standard.

Refractive index. Although no significant differences were observed among the FAME produced by different transesterification methods, the refractive index of the samples decreased by increasing the FAME production from triglycerides (weight efficiency), which resulted from the direct relationship between the refractive index and the length of the carbon chain. The lowest amount of FAME production and the highest refractive index were observed in samples produced by the MSAT method, whereas the highest FAME production and the lowest refractive index were observed in samples produced by the MAT method.

Color attributes. The color characteristics of FAME obtained by different transesterification methods are listed in Table 5. Accordingly, FAME obtained from the MAT method were more visually transparent than the other transesterification methods. FAME produced by MAT had the lowest a* and b* values.

3.3.3. Thermal properties
 

Table 6 shows variations in thermal properties of the produced FAME with respect to different transesterification methods. There were no significant differences among different transesterification methods in terms of ignition and fire points (combustion points), but they differed from each other in terms of the drop and cloud points. The lower pour point of FAME produced by MAT, compared to other transesterification methods, indicates that they remained liquid at a lower temperature and were pumped more easily. After MAT, FAME produced by OAT and UPAT had the lowest drop points, respectively. There were no significant differences between the drop points in the UBAT and MSAT methods. Our results are consistent with previous findings on the transesterification of soybean oil using MSAT and MAT methods. The pour point of the MAT method was -18 °C, whereas the pour point of the MSAT method was -9 °C (Kanitkar et al., 2011Kanitkar A, Balasubramanian S, Lima M, Boldor D. 2011. A critical comparison of methyl and ethyl esters production from soybean and rice bran oil in the presence of microwaves. Bioresour. Technol. 102, 7896–7902. http://doi.org/10.1016/j.biortech.2011.05.091). The lower pour point in MAT can be justified by the complete progress of the transesterification reaction as well as a kinematic viscosity reduction of the produced FAME, compared to the MSAT method. Regarding the cloud point, the optimal conditions for producing FAME by the MAT, UPAT, and UBAT methods showed the lowest crystal formation, temperature and a cloudy state, respectively. The cloud points of the produced FAME are consistent with previous results by Supalakpaniya et al., which involved measuring the cloud point of the FAME produced by MAT from crude palm oil and resulted in a cloud point at -8 °C (Suppalakpanya et al., 2010Suppalakpanya K, Ratanawilai SB, Tongurai C. 2010. Production of ethyl ester from crude palm oil by two-step reaction with a microwave system. Fuel 89, 2140–2144. https://doi.org/10.1016/j.fuel.2010.04.003).

TABLE 6.  Effects of different transesterification methods on heating properties of sour cherry kernel oil fatty acid methyl esters.
Heating property (ºC) Transesterification method
Microwave Ohmic Ultrasonic probe Ultrasonic bath Magnetic stirrer
Flash point 177.00±8.85a* 185.00±9.25a 175.00±8.75a 177.00±8.85a 170.00±8.50a
Fire point 197.00±9.85a 190.00±9.50a 185.00±9.25a 187.00±9.35a 184.00±9.20a
Cloud point -7.00±0.35a 0.00±0.00d -3.00±0.15b -2.00±0.10c 0.00±0.00d
Pour point -19.00±0.95a -17.00±0.85b -15.00±0.75c -13.00±0.65d -13.00±0.65d

* Mean ± SD (n = 3); Statistical test: ANOVA and multiple comparison of means using Duncan’s multiple range test; In each row, means with different lowercase letters are significantly different (P < 0.05). Constant condition: methanol/oil mole ratio of 12, catalyst concentration of 1.2%, and reaction time of 4 min; microwave power of 300 W, ohmic voltage of 200 V, salt concentration of 0.25%, and ultrasonic probe power of 150 W.

3.3.4. Energy consumption
 

Table 7 shows the equivalent of energy consumption in different biodiesel production methods. The highest and the lowest energy consumptions of the reaction steps were related to the MSAT (227 Wh) and MAT (20 Wh) methods, respectively. The energy consumption of the purification steps of MAT, MST, OAT, UPAT, and UBAT methods were almost equal. According to Table 7, the lowest amount of relative energy consumption was attributed to the MAT method, followed by UPAT, OAT, UBAT, and MSAT methods, respectively.

TABLE 7.  Effects of different transesterification methods on energy consumption of sour cherry kernel oil fatty acid methyl esters.
Energy Consumption Transesterification method
Microwave Magnetic Stirrer Ohmic Ultrasonic probe Ultrasonic bath
Optimal time (min) 4 120 4 10 40
Transesterification reaction (Wh) 20 227 53 25 100
Separation of methanol (Wh) 63 63 63 63 63
Washing (Wh) 8 8 8 8 8
Drying (Wh) 71 71 71 71 71
Total (Wh) 162d* 369a 195c 167d 242b
Relative energy consumption (Wh/g) 6.3e 22.5a 9.4c 8.9d 13.9b
CO2 production (g) 129.6d 295.2a 156.2c 133.6d 193.6b
Relative CO2 production 5.0e 18.0a 7.5c 7.1d 11.1b

* Mean ± SD (n = 3); Statistical test: ANOVA and multiple comparison of means using Duncan’s multiple range test; In each row, means with different lowercase letters are significantly different (P < 0.05). Constant condition: methanol/oil mole ratio of 12 and catalyst concentration of 1.2%; microwave power of 300 W, ohmic voltage of 200 V, salt concentration of 0.25%, and ultrasonic probe power of 150 W.

Also, the OAT method reduced the reaction time to some extent due to the homogeneous energy transfer. In the UPAT method, due to the direct effect of the waves on the reactants and its strong mixing effect, the reaction speed was high, and, as a result, the energy consumption was low (Motasemi and Ani, 2012Motasemi F, Ani FN. 2012. A review on microwave-assisted production of biodiesel. Renewable Sustainable Energy Rev. 16, 4719–4733. https://doi.org/10.1016/j.rser.2012.03.069). In addition, the MSAT method emitted the largest amount of CO2 into the environment.

4. CONCLUSIONS

 

The main objective of this study was to investigate the effects of different variables on the transesterification of SCKO with microwaves. In turn, the effects changed the physical and chemical properties of the produced biodiesel and the best possible reaction conditions were determined. The optimal condition of MAT was a mole ratio of 12, 300 W power, KOH concentration of 1.2%, and a transesterification time of 4 min. Also, the FAME produced under optimal microwave conditions were compared to those produced by UPAT, OAT, UBAT, and MSAT methods. The weight efficiency, purity, and final efficiency of FAME produced by MAT were higher than those of other transesterification methods. In comparison with the various transesterification methods, using microwave heating for transesterification significantly reduced the reaction time, energy, and costs.

5. ACKNOWLEDGMENTS

 

This work was financially supported by Shiraz University.

6. DECLARATION OF COMPETING INTEREST

 

The authors of this article declare that they have no financial, professional or personal conflicts of interest that could have inappropriately influenced this work.

7. REFERENCES

 

Alishahi A, Golmakani MT, Niakousari M. 2021. Feasibility Study of Microwave-Assisted Biodiesel Production from Vegetable Oil Refinery Waste. Eur. J. Lipid Sci. Technol. 123, 2000377. https://doi.org/10.1002/ejlt.202000377

AOCS. 2000. Official Methods and Recommended Practices of the American Oil Chemists’ Society (5th Ed.). USA, AOCS Press, Champaign, Illinois.

ASTM. 2013. Standard Specification for Biodiesel Fuel Blend Stock (B100) for Distillate Fuels, ASTM D6751-12.

Almasi S, Najafi G, Ghobadian B, Jalili S. 2021. Biodiesel production from sour cherry kernel oil as novel feedstock using potassium hydroxide catalyst: Optimization using response surface methodology. ISBAB 35, 102089. https://doi.org/10.1016/j.bcab.2021.102089

Atapour M, Kariminia H. 2011. Characterization and transesterification of Iranian bitter almond oil for biodiesel production. Appl. Energy 88, 2377–2381. https://doi.org/10.1016/j.apenergy.2011.01.014

Azcan N, Danisman A. 2008. Microwave assisted transesterification of rapeseed oil. Fuel 87, 1781–1788. http://doi.org/10.1016/j.fuel.2007.12.004

Azcan N, Yilmaz O. 2013. Microwave assisted transesterification of waste frying oil and concentrate methyl ester content of biodiesel by molecular distillation. Fuel 104, 614–619. https://doi.org/10.1016/j.fuel.2012.06.084

Cavalcante KS, Penha MN, Mendonca KK, Louzeiro HC, Vasconcelos AC, Maciel AP, Souza AG, Silva FC. 2010. Optimization of transesterification of castor oil with ethanol using a central composite rotatable design (CCRD). Fuel 89, 1172–1176. https://doi.org/10.1016/j.fuel.2009.10.029

Chen K, Lin Y, Hsu K, Wang H. 2012. Improving biodiesel yields from waste cooking oil by using sodium methoxide and a microwave heating system. Energy 38, 151156. https://doi.org/10.1016/j.energy.2011.12.020

Dehghan L, Golmakani M-T, Hosseini SMH. 2021. Improving biodiesel yield from pre-esterified inedible olive oil using microwave-assisted transesterification method. Grasas Aceites 72, e417. https://doi.org/10.3989/gya.0336201

Dehghan L, Golmakani M-T, Hosseini SMH. 2019. Optimization of microwave-assisted accelerated transesterification of inedible olive oil for biodiesel production. Renew. Energ. 138, 915–922. https://doi.org/10.1016/j.renene.2019.02.017

Golmakani M-T, Dehghan L, Rahimizad N. 2022. Biodiesel production enhanced by ultrasound-assisted esterification and transesterification of inedible olive oil. Grasas Aceites 73, e447. https://doi.org/10.3989/gya.1233202

Gornas P, Rudzinska M, Raczyk M, Misina I, Soliven A, Seglina D. 2016. Composition of bioactive compounds in kernel oils recovered from sour cherry (Prunus cerasus L.) by-products: Impact of the cultivar on potential applications. Ind. Crops Prod. 82, 44–50. https://doi.org/10.1016/j.indcrop.2015.12.010

Kanitkar A, Balasubramanian S, Lima M, Boldor D. 2011. A critical comparison of methyl and ethyl esters production from soybean and rice bran oil in the presence of microwaves. Bioresour. Technol. 102, 7896–7902. http://doi.org/10.1016/j.biortech.2011.05.091

Korlesky NM, Stolp LJ, Kodali DR, Goldschmidt R, Byrdwell WC. 2016. Extraction and characterization of montmorency sour cherry (Prunus cerasus L.) pit oil. J. Am. Oil Chem.’ Soc. 93, 995–1005. http://doi.org/10.1007/s11746-016-2835-4

Leung DYC, Wu X, Leung MKH. 2010. A review on biodiesel production using catalyzed transesterification. Appl. Energy 87, 1083–1095. https://doi.org/10.1016/j.apenergy.2009.10.006

Lin J, Chen Y. 2017. Production of biodiesel by transesterification of Jatropha oil with microwave heating. J. Taiwan Inst. Chem. Eng. 75, 43–50. http://dx.doi.org/10.1016/j.jtice.2017.03.034

Lin Y, Hsu K, Lin J. 2014. Rapid palm-biodiesel production assisted by a microwave system and sodium methoxide catalyst. Fuel 115, 306–311. https://doi.org/10.1016/j.fuel.2013.07.022

Ma F, Hanna MA. 1999. Biodiesel production: a review. Bioresour. Technol. 70, 1–15. https://doi.org/10.1016/S0960-8524(99)00025-5

Mahlinda S, Supardan MD, Husin H, Riza M, Muslim A. 2017. A comparative study of biodiesel production from screw pine fruit seed: using ultrasound and microwave assistance in in-situ transesterification. JESTEC 12, 3412–3425

Motasemi F, Ani FN. 2012. A review on microwave-assisted production of biodiesel. Renewable Sustainable Energy Rev. 16, 4719–4733. https://doi.org/10.1016/j.rser.2012.03.069

Patil PD, Gude VG, Mannarswamy A, Cooke P, Munson-McGee S, Nirmalakhandan N, Lammers P, Deng S. 2011. Optimization of microwave-assisted transesterification of dry algal biomass using response surface methodology. Bioresour. Technol. 102, 1399–1405. https://doi.org/10.1016/j.biortech.2010.09.046

Popa V, Misca C, Bordean D, Raba D, Stef D, Dumbrava D. 2011. Characterization of sour cherries (Prunus cerasus) kernel oil cultivars from Banat. J. Agroaliment. Processes Technol. 15, 398–401.

Sajjadi B, Abdul Aziz AR, Ibrahim S. 2014. Investigation, modelling and reviewing the effective parameters in microwave-assisted transesterification. Renewable Sustainable Energy Rev. 37, 762–777. https://doi.org/10.1016/j.rser.2014.05.021

Sharma A, Kodgire P, Kachhwaha SS. 2019. Biodiesel production from waste cotton-seed cooking oil using microwave-assisted transesterification: Optimization and kinetic modeling. Renewable Sustainable Energy Rev. 116, 109394. https://doi.org/10.1016/j.rser.2019.109394

Suppalakpanya K, Ratanawilai SB, Tongurai C. 2010. Production of ethyl ester from crude palm oil by two-step reaction with a microwave system. Fuel 89, 2140–2144. https://doi.org/10.1016/j.fuel.2010.04.003

Talebian-Kiakalaieh A, Amin NAS, Mazaheri H. 2013. A review on novel processes of biodiesel production from waste cooking oil. Appl. Energy 104, 638–710. http://dx.doi.org/10.1016/j.apenergy.2012.11.061

Yilmaz FM, Görgüç A, Karaaslan M, Vardin H, Bilek SE, Uygun Ö, Bircan C. 2019. Sour Cherry By-products: Compositions, Functional Properties and Recovery Potentials. Crit. Rev. Food Sci. Nutr. 59, 3549–3563. https://doi.org/10.1080/10408398.2018.1496901

Zhang H, Ding J, Zhao Z. 2012. Microwave assisted esterification of acidified oil from waste cooking oil by CERP/PES catalytic membrane for biodiesel production. Bioresour. Technol. 123, 72–77. http://dx.doi.org/10.1016/j.biortech.2012.06.082

Zhang S, Zu Y, Fu Y, Luo M, Zhang D, Efferth T. 2010. Rapid microwave-assisted transesterification of yellow horn oil to biodiesel using a heteropolyacid solid catalyst. Bioresour. Technol. 101, 931–936. http://doi.org/10.1016/j.biortech.2009.08.069

Zu Y, Zhang S, Fu Y, Liu W, Liu Z, Luo M, Efferth T. 2009. Rapid microwave-assisted transesterification for the preparation of fatty acid methyl esters from the oil of yellow horn (Xanthoceras sorbifolia Bunge.). Eur. Food Res. Technol. 229, 43–49. https://doi.org/10.1007/s00217-009-1024-1