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  • 1. 4thInternational Conference on "Advances in Energy Research" Heterogeneous Catalysis for Biodiesel Synthesis and Valorization of Glycerol Presented by Dheerendra Singh Under the guidance of Prof. Sanjay M. Mahajani Prof. Anuradda Ganesh
  • 2. Introduction  Biodiesel is a mixture of fatty acid methyl esters (FAME)  Transesterification of vegetable oils in presence of NaOH/KOH as catalyst  Heterogeneous catalysts have an added advantage i. e. ease of separation ZnO & PbO on zeolite are promising catalysts for producing biodiesel using jatropha oil. Catalysts are characterized by XRD, BET, TEM, SEM and TPD/TPR. The leaching of metal ions is minimized with zeolite as support material.  Glycerol is obtained as a by-product (~10 wt %) in biodiesel production  Mono-glyceride and Glycerol carbonate are synthesized by esterification and transesterification of glycerol. 2 / 18
  • 3. General schematic of reactions considered in the present work Vegetable oil + Methanol Biodiesel + Glycerol Glycerol Fatty acid DMC Mono-glyceride Urea Glycerol carbonate + Methanol Glycerol carbonate + NH3 Urea + Methanol NH3 + CO2 DMC + NH3 Urea 3 / 18
  • 4. Methodology Batch Reactor Materials: Jatropha oil and sunflower oil for Biodiesel Synthesis and oleic acid for esterification of glycerol Catalyst Preparation:  Precipitation  HIP Method1  Modified citrate technique2 Schematic of continuous packed bed reactor 4 / 18
  • 5. Catalyst Characterization MgO (2 2 2) MgO (3 1 1) MgO (2 2 0) MgO MgO (2 0 0) MgO (1 1 1) 1. X-Ray Diffraction ZnO (1 0 3) ZnO (1 1 0) ZnO (1 0 2) ZnO (1 0 1) ZnO (1 0 0) ZnO/ZSM5 ZnO (0 0 2) Intensity (a.u.) PbO/ZSM5 ZSM5 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 2  Two separate phases (ZnO and Zeolite) are observed  The average crystallite size of ZnO is estimated with the help of Scherrer equation and is found to be 22.15 nm.  Intensity of PbO in PbO/ZSM-5 very small 5 / 18
  • 6. 2. Scanning electron microscopy (SEM) SEM imaging of the catalyst ZnO/zeolite, PbO/zeolite and MgO The shape of zeolite (support) particles were non-uniform and the particle size distribution was large with size varying from 50 to 300 nm.  MgO catalyst has porous texture with uniform particle size of 20 nm. 6 / 18
  • 7. Counts Counts 3. Transmission electron microscopy (TEM) 2 14 16 18 20 22 Particle size (nm) 24 26 3 4 5 6 Particle size (nm) 7 TEM imaging of the catalyst ZnO/zeolite, PbO/zeolite and MgO  ZnO particle size varies from 14 nm to 26 nm and the average particle size is 19.54 nm  The particle size of PbO varies from 2.9 nm to 6.8 nm with an average particle size of 4.2 nm  Particle size of MgO is ~ 20 nm.
  • 8. 1. Biodiesel synthesis 100 90 Performance Evaluation of 3ZnO/ZSM-5 catalyst in batch and continuous reactors Wt % of components 80 The conversion of jatropha oil and the yield of biodiesel using ZnO/zeolite and PbO/zeolite are found to be approximately 100 % and 93.8 % at 70 60 50 Wt% MG Wt% FFA Wt% DG Wt% TG Wt % BD 40 30 20 10 0 optimum reaction conditions. 0 10 20 30 40 50 60 Time (min) [Oil (Jatropha): Methanol 1:30, Temperature 200 C, Catalyst loading 0.50 wt %, RPM 500] 90 Zn/Pb (ppm) Not detected >1238.15 920.575 614.033 127.523 PbO powder Zn leaching (ppm) Sample Blank (perchloric acid) ZnO powder ZnO/γ-alumina ZnO/α-alumina ZnO/ZSM-5 90 80 Comparison of Zn/Pb leaching on different supports 100 80 70 70 60 60 TG conversion 50 Zn leaching 40 50 40 30 30 >3400 20 20 PbO/γ-alumina >464 10 10 PbO/β-zeolite 9.29 0 0 0 50 100 150 200 250 300 Time (hr) [4] Singh et al. (under review) 8 / 18 [Reaction temperature, 200°C; methanol: jatropha oil molar ratio, 6:1] % TG conversion 100
  • 9. 4. Thermal program method ZSM-5 TPD of ZSM-5 and ZnO/ZSM-5 0 100 200 300 400 500 600 700 800 TCD Signal Metal support interaction ZnO/ZSM-5 900 30 % PbO/ZSM-5 0 25 % PbO/ZSM-5 100 200 300 400 500 o TPR of PbO supported catalyst Temperature ( C) 25 % PbO/Alumina PbO 0 100 200 300 400 500 600 o Temperature C 700 800 900 9 / 18 600
  • 10. 2. Esterification of oleic acid with glycerol  Mono-glyceride is a good surfactant and has a wide range of applications as emulsifier in food, pharmaceutical, and cosmetic industries.  Reaction can take place even in the absence of catalyst but zeolite alone does not show any catalytic activity. ZnO supported on zeolite shows a significant rise in the reaction rate Product can be formed through parallel or series reaction pathway O OH O OH + R O O C C R O C O C OH Glycerol OH Oleic acid R O C O R MG , OH R + n H2O O , DG R C O OH OH O O C R O TG 10 / 18
  • 11. 100 Esterification of glycerol with oleic acid 90 80 Conversion % 70  Esterification of oleic acid exhibited selectivity 60 50 without catalyst 40 with zeolite 30 as high as 70-80 % for mono-glyceride in the 2.0 wt % ZnO 20 2 wt % ZnO Zeolite 10 conversion range 60-90 %. Amberlyst 35 0 0 100 200 Time (min)  The results indicate that the zeolite supported 400 100 catalyst is equally active as ZnO powder. 90 Both mono-and di-glyceride concentrations 80 70 Selectivity % increase with time 300 60 50 40 30 20 10 0 15 [5] Singh et al. (2013) 25 35 without catalyst (MG) ZnO/Zeolite (MG) ZnO (DG) with zeolite (TG) amberlyst 35 (MG) 45 55 65 conversion %OA with zeolite (MG) Without catalyst (DG) ZnO/Zeolite (DG) ZnO (TG) amberlyst 35 (DG) 75 85 95 ZnO (MG) with Zeolite (DG) without cat (TG) ZnO/Zeolite (TG) Amberlyst 35 (TG) 11 / 18 (Gly:OA mole ratio 4:1; Reaction temperature 150 °C; zeolite, Amberlyst 35 and ZnO loading 2.0 wt % each)
  • 12. 3. Synthesis of glycerol carbonate (GC)  Glycerol carbonate has wide usage in adhesive, surfactant, and elastomer production The conventional method for GC synthesis is by direct carbonation of glycerol with phosgene or carbon monoxide and oxygen  Green way: with Glycerol and Di-methyl Carbonate (DMC) or with Glycerol and Urea O NH2 OH HO OH + H2N Catalyst -NH3 O Glycerol NH2 OH HO Catalyst -NH3 O O Urea O O OH Glycerol carbonate O O O H3C OH CH3 + HO O O Dimethyl carbonate Catalyst OH -CH3OH H3C O Glycerol HO O OH Catalyst -CH3OH O O OH Glycerol carbonate 12 / 18
  • 13. 80 Synthesis of glycerol carbonate With Urea and Glycerol  Without catalyst, glycerol conversion was 39 % after 6 hr. Glycerol conversion % 70 60 50 40 30 With out catalyst 20 ZnO 10  Catalytic performance of MgO is better MgO 0 0 than ZnO 1 2 3 Time (hr) 4 5 6 (Reaction condition: Temp 140oC, cat. loading 0.5 wt %, Urea: glycerol mol ratio 1.4:1)  No by-product formed in the reaction 100  Another value added product, Glycidol is formed in the reaction.  There is observed dependency of selectivity for GC on molar feed ratio of DMC to glycerol 90 80 Conversion % Glycerol With DMC and Glycerol 70 60 50 40 150 C 30 160 C 20 170 C 10 180 C 0 0 1 2 Time (hr) 3 4 5 (DMC : glycerol molar ratio 4:1, catalyst (MgO) loading 0.5 wt % ) 13 / 18
  • 14. 4. Synthesis of DMC from methanol and urea  Di-methyl carbonate (DMC) is an important, environmentally benign building block and is widely used in industry. (2009, world production capacity was 1.8 x 1014 lit/day)  Conventionally DMC was manufactured from phosgene and methanol.  Synthesis of DMC using urea and methanol is an attractive alternative route (1) Slow step thus need cat. (2) (3) 14 / 18
  • 15. Synthesis of DMC Time (hr) 1 2 4 6 DMC yield 0.63 0.83 1.08 2.14 MC yield 86 86.27 87 87 (Reaction temp 180 oC, Methanol/Urea 15, (ZnO/ZSM5) catalyst loading 1 wt %) 18 g molecular sieve with (Si/Al 2.5, acidic Zeolite) was used to absorb the ammonia formed during the reaction. Amberlyst 36 A maximum 6.7 % yield of DMC was obtained in this case. Glass beads (4 mm) 15 / 18
  • 16. Conclusion  ZnO/zeolite, PbO/zeolite catalysts have exhibited good performance in biodiesel synthesis using vegetable oils  Glycerol obtained as a byproduct can be used further in many useful reactions. Mono-glyceride can be synthesized by esterification of glycerol with fatty acid.  Esterification of oleic acid showed selectivity as high as 70-80 % for mono-glyceride in the conversion range 60-90 %. The performance of MgO in the synthesis of glycerol carbonate via urea glycerol and DMC glycerol route is better than ZnO. A maximum of 6.7 % yield of DMC was obtained in the reaction of urea and methanol, which may further increase by continuous and efficient removal of ammonia. 16 / 18
  • 17. References [1] Lu, W., Lu, G., Luo, Y. and Chen, A. (2002) A novel preparation method of ZnO/MCM-41 for hydrogenation of methyl benzoate, Journal of Molecular Catalysis A: Chemical, 188(1), pp. 225–231. [2] Chen, L., Sun, X., Liu, Y. and Li, Y. (2004) Preparation and characterization of porous MgO and NiO/MgO nano composites, Applied Catalysis A: General, 265, pp. 123–128. [3] Mahajani, S. M., Ganesh, A., Singh, D. K. and Gupta, P. D. (2010) Heterogeneous acid catalyst for producing biodiesel from vegetable oils and process for the preparation thereof, Indian Patent Application No 2134/MUM/2010. [4] Singh, D., Bhoi, R., Ganesh, A. and Mahajani, S. M. (2013) Synthesis of Biodiesel from vegetable oil Using supported metal oxide catalyst. Applied catalysis A: General, under review [5] Singh, D., Patidar, P., Ganesh, A. and Mahajani, S. M. (2013) Esterification of oleic acid with glycerol in the presence of supported zinc oxide as catalyst, Industrial and Engineering Chemistry Research, 52 (42), pp.14776-14786 17 / 18
  • 18. Thank you 18 / 18