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Use of CaO and Na3PO4 Catalysts in the Synthesis of Biodiesel and Investigation of Fuel Properties
Available online at www.sciencedirect.com
ScienceDirect Materials Today: Proceedings 4 (2017) 11111–11117
www.materialstoday.com/proceedings
AMMMT 2016
Use of CaO and Na3PO4 Catalysts in the Synthesis of Biodiesel and Investigation of Fuel Properties S.B. Arun a*, R.Suresh a, K.V. Yatish b, B.R. Omkareshc, N.Channa Keshava Naik d a*a,c,d
Department of Mechanical Engineering, Siddaganga Institute of Technology,Tumkur, Karnataka, India. b Department of Chemistry, Siddaganga Institute of Technology, Tumkur, Karnataka, India.
Abstract This study involves separation of Fatty acid methyl ester from non-consumable oil seeds like aegle marmelos, Terminalia belerica, Garcinia gummi-gutta by means of transesterification reaction with KOH and NaOH as homogeneous base catalyst and calcinated CaO and Na3PO4 as a heterogeneous base catalyst. The catalysts CaO and Na3PO4 were characterized by powder Xray diffraction (PXRD). Fuel properties of produced biodiesel were determined. Percentage yield of fatty acid methyl ester using different catalysts was compared with each other.
© 2017 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of Advanced Materials, Manufacturing, Management and Thermal Science (AMMMT 2016). Keywords: CaO, Na3PO4, Fatty acid methyl esters and PXRD
1. Introduction Biodiesel is treated as good substitute fuel with its decreased rate of exhaust emissions, better lubricity, high flash point, abate toxicity and excellent biodegradability over regular diesel. Production of bio fuels from the nonrenewable sources and using these bio fuels as substitute for petroleum products is very advantageous. Bio diesel is a renewable energy source which can be synthesized from vegetable oil and animal fat through chemical reaction called transesterification [1]. Biodiesel is free from sulphur. The main advantage of biodiesel is reduction of emissions of carbon monoxide, sulphur dioxide, un burnt hydrocarbon, and particulate emissions when compared to diesel fuel. The expected energy demand in India for next few couple of decade’s is 5.3%.The production of crude oil in our country can meet only 30-35% of the national utilization and rest we are importing from other countries [2]. Major drawback of Fatty acid methyl ester is high rate of production cost in contrast with diesel production cost which is obtained from petroleum products yet cost of production can be reduced by adopting advanced method of * Corresponding author. Tel.: +91 9731104711 E-mail address:[email protected] 2214-7853© 2017 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of Advanced Materials, Manufacturing, Management and Thermal Science (AMMMT 2016).
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production process. Basically there are two main categories of catalysts such as heterogeneous and homogeneous catalyst [3]. Reaction rate is very rapid in transesterification reaction in the presence of homogeneous alkali catalysts. However, enormous quantity of water is necessary to wash down the formed biodiesel. During this process, a huge amount of waste water having liquids of high acidity or basicity is released which are not environment friendly. Nowadays heterogeneous catalysts is more preferred because of its easy purification and separation of the ultimate obtained products. Aegle marmelos belongs to a Rutaceae family. It is developed over all India and as well as in Asian countries, its seeds has around 35-38 % of oil. Terminalia belerica belongs to a Combretaceae family and its oil content is 40-45 %. Garcinia gummi-gutta seed is the one of energy source in the form biofuel. Garcinia gummi-gutta tree belongs to the family of Clusiaceae, and it is commonly seen in the western ghats of India and forests of Nigeria and seed kernels contain about 30-40 % of oil. The heterogeneous acid, base and enzyme catalyst are used for the transesterification process. Heterogeneous base catalyst process is recyclable and fewer disposal problems [4-6]. Nomenclature CaO NaOH Na3PO4 KOH PXRD
calcium oxide sodium hydroxide Sodium phosphate potassium hydroxide powder x-ray diffraction
2. Materials and methods 2.1 Materials From Bannerghatta forest, Bangalore, Karnataka, India the non edible seeds like Terminalia belerica and from Biofuel, I&D Centre, SIT, Tumkur, Karnataka, India a Garcinia gummi-gutta seeds were collected. The NAOH, KOH, Cao and methyl alcohol were usally obtained from Fisher Scientifics .By subjecting seeds to expeller an oil can be extracted [7]. Prior to transesterification reaction, the catalysts calcium oxide and sodium phosphate were dried out in a warm air oven at about 125 oC for 12 hours and that can be calcinied in a muffle furnace at 605 oC for five hours. 2.2 Transesterification reaction This reaction was conducted out in a 1Litre capacity 3-neck flask which is fitted with a condenser at the top. Simple thermometer was used to measure the reaction temperature. Round bottom flask having the reaction mixture was placed on a magnetic stirrer equipped with digital rpm and temperature controller. For both homogeneous catalyst and heterogeneous catalyst the reaction mixture of 60 oC is kept and is blend at a invariable speed of 600 rpm constantly, 1:6 oil molar to methanol ratio and 1% wt/v of potassium hydroxide and sodium hydroxide catalysts were used, reaction was carried out about for 90 minutes. For heterogeneous catalysts, 1:9 oil to methanol ratio and 2% wt/v of Na3PO4 and CaO catalysts were used, reaction was carried out for about 180 minutes. Then the reaction mixture is subjected to separating funnel to settle for about 9-10 hours. Biodiesel and Glycerine were separated in homogeneous catalyzed reaction and whereas the catalyst, glycerine and biodiesel were separated in heterogeneous catalyzed reaction [8]. 2.3 Washing and Drying Washing is a process of removing the excess basicity or acidity, soaps, entrained glycerol and excess methanol. The biodiesel obtained after transesterification washed by warm distilled water (50 oC) till the bottom layer had a pH same as the pH of distilled water representing that biodiesel is free from catalyst. Fatty acid methyl ester which is obtained after washing is made to heat to about 100˚C by subjecting in to rota mantel so that water content can be easily removed from the biodiesel [9].
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2.4 Decalcification Decalcification was done only for heterogeneous catalyst biodiesel production method and it was carried out by adding the complexing agent such as citric acid. The complexing agent absorbs the catalyst content and also absorbs the impurities from the biodiesel. The methanol from the biodiesel can be recovered from distillation [10]. 3. Results and discussion 3.1 Catalysts Characterization
In te n sity (a .u )
CaO
Na3PO4
10
20
30
40
50
60
70
2θ (degrees)
Figure 1. PXRD of Sodium phosphate and Calcium oxide The PXRD patterns of calcium oxide and Sodium phosphate are shown in Figure1. PXRD pattern of Calcium oxide consisted of diffraction peaks corresponding to both Calcium oxide and Ca (OH) 2. However, the Ca (OH) 2 peaks are considerably smaller than those of the CaO. Therefore, in these particles, Ca (OH)2 might not be completely decomposed to CaO [11]. PXRD pattern consisted of peaks pertaining to tetragonal phase corresponding to CaO. In Na3PO4, the diffraction peaks are well indexed monoclinic Na3PO4 (JCPDS card no.201150). The maximum intensities observed in sodium phosphate are 271, 495, and 268 at 21.1o, 34.5o, and 35.48o respectively. The average crystalline size at 47.063 nm shows strong basic character in the sodium phosphate. 3.2 Fuel properties Table-1: Fuel properties of various biodiesel obtained using homogeneous catalyst. Using NaOH Using KOH Biodiesel Properties Standard Range AMME TBME GGME AMME TBME GGME Kinematic Viscosity ASTM D446 1.8-6.2 5.2 5.75 5.8 5.18 5.71 5.85 (Cst) at 40°C Flash point (°C) ASTM D93 >130 151 176 174 154 173 178 ASTM 3 870-900 886 888 887 880 890 889 Density (Kg/m ) D4052 Ash, %w/w ASTM D874 0.020 max Nil Nil Nil Nil Nil Nil Carbon residue ASTM 0.050 max Nil Nil Nil Nil Nil 0.02 %w/w D4530 The properties of homogeneous and heterogeneous catalyzed biodiesels were in the range of American Society for Testing and Materials (ASTM) as shown in the table 1 and table 2 [12]. Kinematic viscosity, flash point and density of AMME were less compared to other biodiesels and GGME has high values. 0.023% of ash was present in AMME using CaO catalyst however the ash content was not present in the rest of the biodiesels and 0.02% of carbon residue was present in GGME using KOH catalyst. Among these biodiesels, the values of AMME were close to diesel compared to TBME and GGME [13].
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Table-2: Fuel properties of various biodiesel obtained using heterogeneous catalyst. Using CaO Using Na3PO4 Biodiesel Properties Standard Range AMME TBME GGME AMME TBME GGME Kinematic Viscosity ASTM D446 1.8-6.2 4.8 5.9 5.93 4.92 5.93 5.9 (Cst) at 40°C Flash point (°C) ASTM D93 >130 155 175 181 163 178 184 ASTM 870-900 875 887 890 885 895 897 Density (Kg/m3) D4052 0.020 Nil Nil Nil Nil Nil Nil Ash, % mass ASTM D874 max Carbon residue % ASTM 0.050 0.023 Nil Nil Nil Nil Nil mass D4530 max 3.2.1. Kinematic viscosity
5.5
Using NaOH Using KOH Using CaO Using Na3PO4
4.5
6.0
Using Using Using Using
5.5 Kinematic viscosity (Cst)
Kinematic viscosity (Cst)
5.0
4.0 3.5 3.0 2.5
5.0
NaOH KOH CaO Na3PO4
4.5 4.0 3.5 3.0 2.5
Diesel
B10
B20
B30
B40
B50
B100
Diesel
B10
Blended proportions
Figure 2. Kinematic viscosity(cSt) of aegle marmelos biodiesel and its blend with diesel
6.0
B30
B40
B50
B100
Figure 3. Kinematic viscosity (cSt) of terminaliabeleric and its blend with diesel
Using NaOH Using KOH Using CaO Using Na3PO4
5.5 Kinematic viscosity (Cst)
B20
Blended proportions
5.0 4.5 4.0 3.5 3.0 2.5 Diesel B10
B20
B30
B40
B50
B100
Blended proportions
Figure 4. Kinematic viscosity(cSt) of Garcinia gummi-gutta biodiesel and its blends with diesel Kinematic viscosity of various biodiesels produced using a homogeneous and heterogeneous catalyst is shown in figure 2, 3 and 4. In all biodiesels the viscosity (cSt) raises with increase in blending, which is represented in the figure 2, 3 and 4. The viscosity of aegle marmelos biodiesel obtained by using a homogeneous catalyst is
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higher than the heterogeneous catalyst, but the viscosity of terminalia belerica and garcinia gummi-gutta biodiesel obtained by using a heterogeneous catalyst higher than the homogeneous catalyst. Among heterogeneous catalyst, the viscosity of biodiesel obtained using CaO is higher than Na3PO4. In a homogeneous catalyst, the viscosity of biodiesel obtained using NaOH is higher than KOH. Less value of viscosity achieved in aegle marmelos biodiesel compared to terminalia belerica and garcinia gummi-gutta biodiesel by using both types of catalysts [14-17]. 3.2.2 Flash point
180
140
o
120 100 80 60 40
Using NaOH Using KOH Using CaO Using Na3PO4
160 Flash point ( C)
o
Flash point ( C)
180
Using NaOH Using KOH Using CaO Using Na3PO4
160
140 120 100 80 60
Diesel B10
B20
B30
B40
B50
B100
40
Blended proportions
Diesel B10
B20
B30
B40
B50
B100
Blended proportions
Figure 5. Flash point of aegle marmelos biodiesel and blending of aegle marmelos biodiesel with diesel
Figure 6. Flash point of terminaliabelerica biodiesel and blending of terminaliabelerica biodiesel with diesel
200 Using NaOH Using KOH Using CaO Using Na3PO4
180
140
o
Flash point ( C)
160
120 100 80 60 40
Diesel
B10
B20
B30
B40
B50
B100
Blended proportions
Figure 7. Flash point of Garcinia gummi-gutta biodiesel and blending of Garcinia gummi-gutta biodiesel with diesel It is one of the important parameter for biodiesel because regarding storage and transport it makes the biodiesel more safer. The flash point of various biodiesels produced using homogeneous and heterogeneous catalyst is shown in figure 5, 6 and 7. The flash point of various biodiesels obtained is high (>150 oC) when compared to diesel. The flash point of all biodiesels obtained using a heterogeneous catalyst is higher than the homogeneous catalyst. Among heterogeneous catalyst, the flash point of biodiesels obtained using Na3PO4 is higher than CaO. Less value of flash point was achieved in aegle marmelos biodiesel compared to terminaliabelerica and garcinia gummi-gutta biodiesel by using both types of catalysts [18]. 3.2.3 Density It is one of the important parameter for biodiesel because regarding storage and transport it makes the biodiesel more safer. The flash point of various biodiesels produced using homogeneous and heterogeneous catalyst is shown in figure 8, 9 and 10. The flash point of various biodiesels obtained is high (>150 oC) when compared to diesel. The flash point of all biodiesels obtained using a heterogeneous catalyst is higher than the homogeneous catalyst. Among heterogeneous catalyst, the flash point of biodiesels obtained using Na3PO4 is higher than CaO. Less value of flash point was achieved in aegle marmelos biodiesel compared to terminalia belerica and garcinia gummi-gutta biodiesel by using both types of catalysts [19].
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900
890
Using NaOH Using KOH Using CaO Using Na3PO4
860
880 -3
-3
Density (Kg m )
870
850 840 830
870 860 850 840 830
820
820
810
810
Diesel B10
B20
B30
B40
B50
Diesel B10
B100
Figure 8. Flash point of aegle marmelos biodiesel and blending of aegle marmelos biodiesel with diesel
880 -3
B30
B40
B50
B100
Figure 9. Flash point of terminalia belerica biodiesel and blending of terminalia belerica biodiesel with diesel
Using NaOH Using KOH Using CaO Using Na3PO4
890
Density (Kg m )
B20
Blended proportions
Blended proportions
900
Using NaOH Using KOH Using CaO Using Na3PO4
890
Density (Kg m )
880
870 860 850 840 830 820 810 Diesel B10
B20
B30
B40
B50
B100
Blended proportions
Figure 10. Density of Garcinia-gummi gutta and its blends with diesel. 4. Conclusion The present work shows that NaOH, KOH, CaO and Na3PO4 are suitable catalysts for production of biodiesel. CaO and Na3PO4 can be recovered and reused. The kind of glycerin obtained from CaO and Na3PO4 is high in comparison to NaOH and KOH. The percentage yield of biodiesels obtained by using a heterogeneous catalyst (CaO and Na3PO4) is more than homogeneous catalyst (NaOH and KOH) [20]. The kinematic viscosity and flash point of aegle marmelos fatty acid methyl ester obtained using both type of catalyst is less compared to terminaliabelerica and garcinia gummi-gutta biodiesel, but densities of all biodiesels are near to each other. The fuel properties of each biodiesel that is produced are very high when compared to conventional diesel. Hence these biodiesels can be used as blends with diesel with suitable proportions to achieve CI engine specification range [21].
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References: 1) Gui, M., Bhatia, S., 2007.usefullness of consumable oil v/s non-consumable oil v/s waste consumable oil as biodiesel feedstock. Energy. 33, 1646–53. 2) Fangrui Ma., Hanna, A., 1999. Fatty acid methyl ester production: a review. Bior. Techno. 70, 1-15. 3) Maumita Chakraborty, Konwer.,2009. Investigation of terminalia (Terminalia belerica Robx.) seed oil as prospective biodiesel source for North-East India. Fuel. Proce. Techno. 90, 1435–1441. 4) Rakesh Sarin.,Arif Ali Khan., 2010. Terminalia belerica Roxb. seed oil: A potential biodiesel resource. Biore. Techno. 101, 1380-1384. 5) Dhanamurugan, A., Subramanian, R., 2015. Effect of injection timing on a diesel engine fueled with bael biodiesel. J. Scien. Indus. Rese. 74, 232-235. 6) Ramesh Bujari, S., Sharanappa Godiganur., 2014. Sour Garcinia (Garcinia Gummigutta) as a Source of Biodiesel in India. Intern. J. Scient. Engine. 5, 364. 7) Predojevic, 2010. The production Fatty acid methyl ester from waste oils: a comparison of dissimilar refinement steps. Fuel. 56, 9734–5462. 8) Kusakabe., Yamasaki, S., Guan, G. 2008. Production of Tri-potassium phosphate by means of unused cooking oil. Fuel. Proce. Techno. 90, 985–674. 9) Zabeti, M., Aroua, M.K., 2008. Optimization of the activity of CaO/Al2O3 catalyst for fatty acid methyl ester production using RSM. Appl. Catal. A: Gene. 366, 154–132. 10) Kouzu, M., Tajika, M., Sugimoto, Hidaka, J., 2009. Soybean Biodiesel production Using Cao as catalyst. Fuel.87, 2712–5606. 11) Kansedo, J., Bhatia, S., 2009. Productionof fatty acid methyl ester from palm oil using heterogeneous transesterification. Biom. and Bioene. 23, 291–673. 12) Kouzu, M., Tajika, M., Sugimoto, Hidaka, J., 2009. Soybean Biodiesel production Using Cao as catalyst. Fuel. 87, 2712–5606. 13) Katsoulidis, A.P., Kontominas, M.G., 2009. Transesterification of soybean oil to fatty acid methyl ester by means of heterogeneous catalysts. Fuel. Proce. Techno. 91, 674–676. 14) Arzamendi, G., Gandía, L.M., 2007. Synthesis of biodiesel by using heterogeneous sodium hydroxide/alumina catalysts: Chemi. Engine. J. 123–130. 15) Albuquerque, M.C.G., Santamaría-González, J., Moreno-Tost, R., Jiménez-López, A., Cavalcante C.L., 2008. Cao supported on mesoporous silicas as basic catalysts for transesterification reactions. 16) Shimada, Y., Sugihara, A., 2002. Enzymatic alcoholysis for biodiesel fuel production and application of reaction to oil processing. J. Mol. Catal. B: Enzym. 17, 133-42. 17) Liu, X., He, H., Wang, Y., Zhu, S., Piao, X., 2008. Transesterification of soybean oil to biodiesel using CaO as a solid base catalyst. Fuel. 87, 216-21. 18) Tate, R., Allen, C.A., Walki, K.I., 2009. Determination of density upto 350 oC of three fatty acid methyl ester. Fuel. 85, 1004-9. 19) Arun, S.B., Suresh, R., Yatish, K.V., 2014. Relative Estimation of Various fuel properties of Mahua and Simarouba Glauca biodiesel having different blends with conventional diesel, Appl. Mecha. Mater. Vols,592-594, pp 724-728. 20) Alptekin, E., Shimada, Y., Canakci, M., 2008. Determination of density and viscosity of biodiesel-conventional diesel fuel blend. Renew. Ener. 33, 2623-30. 21) Anand, K.K., Singh, B., Chandan, B.K., Bharadwaj V., 1998. Trihydroxy benzoic acid the heptoprotective principle in the fruits of Terminalia belerica Rese. 36, 315-321.
ScienceDirect Materials Today: Proceedings 4 (2017) 11111–11117
www.materialstoday.com/proceedings
AMMMT 2016
Use of CaO and Na3PO4 Catalysts in the Synthesis of Biodiesel and Investigation of Fuel Properties S.B. Arun a*, R.Suresh a, K.V. Yatish b, B.R. Omkareshc, N.Channa Keshava Naik d a*a,c,d
Department of Mechanical Engineering, Siddaganga Institute of Technology,Tumkur, Karnataka, India. b Department of Chemistry, Siddaganga Institute of Technology, Tumkur, Karnataka, India.
Abstract This study involves separation of Fatty acid methyl ester from non-consumable oil seeds like aegle marmelos, Terminalia belerica, Garcinia gummi-gutta by means of transesterification reaction with KOH and NaOH as homogeneous base catalyst and calcinated CaO and Na3PO4 as a heterogeneous base catalyst. The catalysts CaO and Na3PO4 were characterized by powder Xray diffraction (PXRD). Fuel properties of produced biodiesel were determined. Percentage yield of fatty acid methyl ester using different catalysts was compared with each other.
© 2017 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of Advanced Materials, Manufacturing, Management and Thermal Science (AMMMT 2016). Keywords: CaO, Na3PO4, Fatty acid methyl esters and PXRD
1. Introduction Biodiesel is treated as good substitute fuel with its decreased rate of exhaust emissions, better lubricity, high flash point, abate toxicity and excellent biodegradability over regular diesel. Production of bio fuels from the nonrenewable sources and using these bio fuels as substitute for petroleum products is very advantageous. Bio diesel is a renewable energy source which can be synthesized from vegetable oil and animal fat through chemical reaction called transesterification [1]. Biodiesel is free from sulphur. The main advantage of biodiesel is reduction of emissions of carbon monoxide, sulphur dioxide, un burnt hydrocarbon, and particulate emissions when compared to diesel fuel. The expected energy demand in India for next few couple of decade’s is 5.3%.The production of crude oil in our country can meet only 30-35% of the national utilization and rest we are importing from other countries [2]. Major drawback of Fatty acid methyl ester is high rate of production cost in contrast with diesel production cost which is obtained from petroleum products yet cost of production can be reduced by adopting advanced method of * Corresponding author. Tel.: +91 9731104711 E-mail address:[email protected] 2214-7853© 2017 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of Advanced Materials, Manufacturing, Management and Thermal Science (AMMMT 2016).
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production process. Basically there are two main categories of catalysts such as heterogeneous and homogeneous catalyst [3]. Reaction rate is very rapid in transesterification reaction in the presence of homogeneous alkali catalysts. However, enormous quantity of water is necessary to wash down the formed biodiesel. During this process, a huge amount of waste water having liquids of high acidity or basicity is released which are not environment friendly. Nowadays heterogeneous catalysts is more preferred because of its easy purification and separation of the ultimate obtained products. Aegle marmelos belongs to a Rutaceae family. It is developed over all India and as well as in Asian countries, its seeds has around 35-38 % of oil. Terminalia belerica belongs to a Combretaceae family and its oil content is 40-45 %. Garcinia gummi-gutta seed is the one of energy source in the form biofuel. Garcinia gummi-gutta tree belongs to the family of Clusiaceae, and it is commonly seen in the western ghats of India and forests of Nigeria and seed kernels contain about 30-40 % of oil. The heterogeneous acid, base and enzyme catalyst are used for the transesterification process. Heterogeneous base catalyst process is recyclable and fewer disposal problems [4-6]. Nomenclature CaO NaOH Na3PO4 KOH PXRD
calcium oxide sodium hydroxide Sodium phosphate potassium hydroxide powder x-ray diffraction
2. Materials and methods 2.1 Materials From Bannerghatta forest, Bangalore, Karnataka, India the non edible seeds like Terminalia belerica and from Biofuel, I&D Centre, SIT, Tumkur, Karnataka, India a Garcinia gummi-gutta seeds were collected. The NAOH, KOH, Cao and methyl alcohol were usally obtained from Fisher Scientifics .By subjecting seeds to expeller an oil can be extracted [7]. Prior to transesterification reaction, the catalysts calcium oxide and sodium phosphate were dried out in a warm air oven at about 125 oC for 12 hours and that can be calcinied in a muffle furnace at 605 oC for five hours. 2.2 Transesterification reaction This reaction was conducted out in a 1Litre capacity 3-neck flask which is fitted with a condenser at the top. Simple thermometer was used to measure the reaction temperature. Round bottom flask having the reaction mixture was placed on a magnetic stirrer equipped with digital rpm and temperature controller. For both homogeneous catalyst and heterogeneous catalyst the reaction mixture of 60 oC is kept and is blend at a invariable speed of 600 rpm constantly, 1:6 oil molar to methanol ratio and 1% wt/v of potassium hydroxide and sodium hydroxide catalysts were used, reaction was carried out about for 90 minutes. For heterogeneous catalysts, 1:9 oil to methanol ratio and 2% wt/v of Na3PO4 and CaO catalysts were used, reaction was carried out for about 180 minutes. Then the reaction mixture is subjected to separating funnel to settle for about 9-10 hours. Biodiesel and Glycerine were separated in homogeneous catalyzed reaction and whereas the catalyst, glycerine and biodiesel were separated in heterogeneous catalyzed reaction [8]. 2.3 Washing and Drying Washing is a process of removing the excess basicity or acidity, soaps, entrained glycerol and excess methanol. The biodiesel obtained after transesterification washed by warm distilled water (50 oC) till the bottom layer had a pH same as the pH of distilled water representing that biodiesel is free from catalyst. Fatty acid methyl ester which is obtained after washing is made to heat to about 100˚C by subjecting in to rota mantel so that water content can be easily removed from the biodiesel [9].
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2.4 Decalcification Decalcification was done only for heterogeneous catalyst biodiesel production method and it was carried out by adding the complexing agent such as citric acid. The complexing agent absorbs the catalyst content and also absorbs the impurities from the biodiesel. The methanol from the biodiesel can be recovered from distillation [10]. 3. Results and discussion 3.1 Catalysts Characterization
In te n sity (a .u )
CaO
Na3PO4
10
20
30
40
50
60
70
2θ (degrees)
Figure 1. PXRD of Sodium phosphate and Calcium oxide The PXRD patterns of calcium oxide and Sodium phosphate are shown in Figure1. PXRD pattern of Calcium oxide consisted of diffraction peaks corresponding to both Calcium oxide and Ca (OH) 2. However, the Ca (OH) 2 peaks are considerably smaller than those of the CaO. Therefore, in these particles, Ca (OH)2 might not be completely decomposed to CaO [11]. PXRD pattern consisted of peaks pertaining to tetragonal phase corresponding to CaO. In Na3PO4, the diffraction peaks are well indexed monoclinic Na3PO4 (JCPDS card no.201150). The maximum intensities observed in sodium phosphate are 271, 495, and 268 at 21.1o, 34.5o, and 35.48o respectively. The average crystalline size at 47.063 nm shows strong basic character in the sodium phosphate. 3.2 Fuel properties Table-1: Fuel properties of various biodiesel obtained using homogeneous catalyst. Using NaOH Using KOH Biodiesel Properties Standard Range AMME TBME GGME AMME TBME GGME Kinematic Viscosity ASTM D446 1.8-6.2 5.2 5.75 5.8 5.18 5.71 5.85 (Cst) at 40°C Flash point (°C) ASTM D93 >130 151 176 174 154 173 178 ASTM 3 870-900 886 888 887 880 890 889 Density (Kg/m ) D4052 Ash, %w/w ASTM D874 0.020 max Nil Nil Nil Nil Nil Nil Carbon residue ASTM 0.050 max Nil Nil Nil Nil Nil 0.02 %w/w D4530 The properties of homogeneous and heterogeneous catalyzed biodiesels were in the range of American Society for Testing and Materials (ASTM) as shown in the table 1 and table 2 [12]. Kinematic viscosity, flash point and density of AMME were less compared to other biodiesels and GGME has high values. 0.023% of ash was present in AMME using CaO catalyst however the ash content was not present in the rest of the biodiesels and 0.02% of carbon residue was present in GGME using KOH catalyst. Among these biodiesels, the values of AMME were close to diesel compared to TBME and GGME [13].
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Table-2: Fuel properties of various biodiesel obtained using heterogeneous catalyst. Using CaO Using Na3PO4 Biodiesel Properties Standard Range AMME TBME GGME AMME TBME GGME Kinematic Viscosity ASTM D446 1.8-6.2 4.8 5.9 5.93 4.92 5.93 5.9 (Cst) at 40°C Flash point (°C) ASTM D93 >130 155 175 181 163 178 184 ASTM 870-900 875 887 890 885 895 897 Density (Kg/m3) D4052 0.020 Nil Nil Nil Nil Nil Nil Ash, % mass ASTM D874 max Carbon residue % ASTM 0.050 0.023 Nil Nil Nil Nil Nil mass D4530 max 3.2.1. Kinematic viscosity
5.5
Using NaOH Using KOH Using CaO Using Na3PO4
4.5
6.0
Using Using Using Using
5.5 Kinematic viscosity (Cst)
Kinematic viscosity (Cst)
5.0
4.0 3.5 3.0 2.5
5.0
NaOH KOH CaO Na3PO4
4.5 4.0 3.5 3.0 2.5
Diesel
B10
B20
B30
B40
B50
B100
Diesel
B10
Blended proportions
Figure 2. Kinematic viscosity(cSt) of aegle marmelos biodiesel and its blend with diesel
6.0
B30
B40
B50
B100
Figure 3. Kinematic viscosity (cSt) of terminaliabeleric and its blend with diesel
Using NaOH Using KOH Using CaO Using Na3PO4
5.5 Kinematic viscosity (Cst)
B20
Blended proportions
5.0 4.5 4.0 3.5 3.0 2.5 Diesel B10
B20
B30
B40
B50
B100
Blended proportions
Figure 4. Kinematic viscosity(cSt) of Garcinia gummi-gutta biodiesel and its blends with diesel Kinematic viscosity of various biodiesels produced using a homogeneous and heterogeneous catalyst is shown in figure 2, 3 and 4. In all biodiesels the viscosity (cSt) raises with increase in blending, which is represented in the figure 2, 3 and 4. The viscosity of aegle marmelos biodiesel obtained by using a homogeneous catalyst is
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higher than the heterogeneous catalyst, but the viscosity of terminalia belerica and garcinia gummi-gutta biodiesel obtained by using a heterogeneous catalyst higher than the homogeneous catalyst. Among heterogeneous catalyst, the viscosity of biodiesel obtained using CaO is higher than Na3PO4. In a homogeneous catalyst, the viscosity of biodiesel obtained using NaOH is higher than KOH. Less value of viscosity achieved in aegle marmelos biodiesel compared to terminalia belerica and garcinia gummi-gutta biodiesel by using both types of catalysts [14-17]. 3.2.2 Flash point
180
140
o
120 100 80 60 40
Using NaOH Using KOH Using CaO Using Na3PO4
160 Flash point ( C)
o
Flash point ( C)
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Using NaOH Using KOH Using CaO Using Na3PO4
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B20
B30
B40
B50
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40
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Diesel B10
B20
B30
B40
B50
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Figure 5. Flash point of aegle marmelos biodiesel and blending of aegle marmelos biodiesel with diesel
Figure 6. Flash point of terminaliabelerica biodiesel and blending of terminaliabelerica biodiesel with diesel
200 Using NaOH Using KOH Using CaO Using Na3PO4
180
140
o
Flash point ( C)
160
120 100 80 60 40
Diesel
B10
B20
B30
B40
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Blended proportions
Figure 7. Flash point of Garcinia gummi-gutta biodiesel and blending of Garcinia gummi-gutta biodiesel with diesel It is one of the important parameter for biodiesel because regarding storage and transport it makes the biodiesel more safer. The flash point of various biodiesels produced using homogeneous and heterogeneous catalyst is shown in figure 5, 6 and 7. The flash point of various biodiesels obtained is high (>150 oC) when compared to diesel. The flash point of all biodiesels obtained using a heterogeneous catalyst is higher than the homogeneous catalyst. Among heterogeneous catalyst, the flash point of biodiesels obtained using Na3PO4 is higher than CaO. Less value of flash point was achieved in aegle marmelos biodiesel compared to terminaliabelerica and garcinia gummi-gutta biodiesel by using both types of catalysts [18]. 3.2.3 Density It is one of the important parameter for biodiesel because regarding storage and transport it makes the biodiesel more safer. The flash point of various biodiesels produced using homogeneous and heterogeneous catalyst is shown in figure 8, 9 and 10. The flash point of various biodiesels obtained is high (>150 oC) when compared to diesel. The flash point of all biodiesels obtained using a heterogeneous catalyst is higher than the homogeneous catalyst. Among heterogeneous catalyst, the flash point of biodiesels obtained using Na3PO4 is higher than CaO. Less value of flash point was achieved in aegle marmelos biodiesel compared to terminalia belerica and garcinia gummi-gutta biodiesel by using both types of catalysts [19].
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900
890
Using NaOH Using KOH Using CaO Using Na3PO4
860
880 -3
-3
Density (Kg m )
870
850 840 830
870 860 850 840 830
820
820
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810
Diesel B10
B20
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Figure 8. Flash point of aegle marmelos biodiesel and blending of aegle marmelos biodiesel with diesel
880 -3
B30
B40
B50
B100
Figure 9. Flash point of terminalia belerica biodiesel and blending of terminalia belerica biodiesel with diesel
Using NaOH Using KOH Using CaO Using Na3PO4
890
Density (Kg m )
B20
Blended proportions
Blended proportions
900
Using NaOH Using KOH Using CaO Using Na3PO4
890
Density (Kg m )
880
870 860 850 840 830 820 810 Diesel B10
B20
B30
B40
B50
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Blended proportions
Figure 10. Density of Garcinia-gummi gutta and its blends with diesel. 4. Conclusion The present work shows that NaOH, KOH, CaO and Na3PO4 are suitable catalysts for production of biodiesel. CaO and Na3PO4 can be recovered and reused. The kind of glycerin obtained from CaO and Na3PO4 is high in comparison to NaOH and KOH. The percentage yield of biodiesels obtained by using a heterogeneous catalyst (CaO and Na3PO4) is more than homogeneous catalyst (NaOH and KOH) [20]. The kinematic viscosity and flash point of aegle marmelos fatty acid methyl ester obtained using both type of catalyst is less compared to terminaliabelerica and garcinia gummi-gutta biodiesel, but densities of all biodiesels are near to each other. The fuel properties of each biodiesel that is produced are very high when compared to conventional diesel. Hence these biodiesels can be used as blends with diesel with suitable proportions to achieve CI engine specification range [21].
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