Efficient Catalytic Synthesis of Glycerol Carbonate Using Optimized Na and K Titanate Nanotubes Catalysts

Abstract:

The synthesis of glycerol carbonate from glycerol has garnered significant research attention because of its wide application in the lithium-ion battery and pharmaceutical industries. This study summarizes the catalytic transformation of glycerol to glycerol carbonate using Na and K titanate nanotubes as catalysts. We report the synthesis of Na and K titanate nanotubes catalyst by a simple co-precipitation route and investigate their catalytic activity in the transesterification of glycerol. The physicochemical properties of the Na and K titanate nanotubes catalyst were successfully studied by CO2-TPD and XRD. The designed catalyst possesses high catalytic efficiency and stability in the transesterification reaction of glycerol. Based on its surface area and basicity, several experiments were performed, and it was observed that under optimized conditions (i.e., 5 wt.% catalyst loading, 5:1 molar ratio of DMC to glycerol, 90 °C, and 90 min), the highest conversion of glycerol was achieved, 92.6% glycerol carbonate. The high thermal stability and recyclability make it an efficient heterogeneous catalyst for the synthesis of glycerol carbonate.

• Periodical: Nano Hybrids and Composites (Volume 43)
• Pages: 87-97
• DOI: https://doi.org/10.4028/p-MyoLP6
• Online since: April 2024
• Authors: M. Malyaadri, K. Jagadeeswaraiah*
• Keywords: DMC, Glycerol, Glycerol Carbonate, Potassium, Sodium Titanate, Titanium Dioxide, Transesterification

References

[1] R.E. Schaak et al., Perovskites by design: a toolbox of solid-state reactions, Chem. Mater. 14(2002) 1455-71.

DOI: 10.1021/cm010689m

[2] M. Aresta et al., study on the carboxylation of glycerol to glycerol carbonate with carbon dioxide: the role of the catalyst, solvent and reaction conditions. J. mol. Catalysis 257(2006)149–153. https://doi.org/10.1016/j.%20molcata.2006.05.021.

DOI: 10.1016/j.molcata.2006.05.021

[3] A. Behr et al., Lindner F Improved Utilisation of Renewable Resources: New Important Derivatives of Glycerol, Green Chem. 10(2008) 13-30.

DOI: 10.1039/b710561d

[4] J.R. Ochoa-Gómez et al., Synthesis of glycerol carbonate from glycerol and dimethyl carbonate by transesterification: catalyst screening and reaction optimization, Appl. Catal. Gen. 366(2009) 315–324.

DOI: 10.1016/j.apcata.2009.07.020

[5] M.O Sonnati et al., Glycerol carbonate as a versatile building block for tomorrow: synthesis reactivity properties and applications, Green Chem. 15(2013) 283–306.

DOI: 10.1039/c2gc36525a

[6] Y. Qing et al., Production of glycerol carbonate using crude glycerol from biodiesel production with DBU as a catalyst, Chine J. Chem. Eng. 26(2018) 1912–1919.

DOI: 10.1016/j.cjche.2018.01.010

[7] S. Ramesh et al., Room temperature synthesis of glycerol carbonate catalyzed by spray dried sodium aluminate microspheres, Catal. Commun. 97(2017) 102–105.

DOI: 10.1016/j.catcom.2017.04.034

[8] E.L. Almeida et al., Production of Biofuels from Glycerol from the Biodiesel Production Process—A Brief Review. Fermentation. 9(10) (2023) 869.

DOI: 10.3390/fermentation9100869

[9] G. P. Deshmukh et al., Tuneable transesterification of glycerol with dimethyl carbonate for synthesis of glycerol carbonate and glycidol on MnO2 nanorods and efficacy of different polymorphs. Molecular Catalysis 515 (2021) 111934.

DOI: 10.1016/j.mcat.2021.111934

[10] Z. Pirzadi et al., From glycerol production to its value-added uses: A critical review, Fuel 329(2022) 125044.

DOI: 10.1016/j.fuel.2022.125044

[11] A. D. Sofía, et al., Layered double hydroxides modified by transition metals for sustainable glycerol valorization to glycerol carbonate, Catalysis Today (2023) 114415.

DOI: 10.1016/j.cattod.2023.114415

[12] M.H.A. Rahim et al., Synthesis of glycerol carbonate from industrial by-products by alcoholysis of urea: Crude glycerol and red gypsum, Fuel 357(2024) 129774.

DOI: 10.1016/j.fuel.2023.129774

[13] S. Sahani et al., Recent advances in bio-glycerol valorization to glycerol carbonate by heterogenous base-catalyzed transesterification, Molecular Catalysis 550 (2023) 113508.

DOI: 10.1016/j.mcat.2023.113508

[14] M.S. Babu et al., Indium exchanged heteropoly tungstates: Efficient catalysts for the synthesis of glycerol carbonate from glycerol and urea, Inorganica Chimica Acta (2023) 121655.

DOI: 10.1016/j.ica.2023.121655

[15] C.M. Scheid et al., Glycerol carbonate synthesis over nanostructured titanate catalysts: Effect of morphology and structure of catalyst, Chemical Engineering Research and Design 197(2023) 392-404

DOI: 10.1016/j.cherd.2023.07.039

[16] S.K. Karmee, A review on preparation and applications of glycerol carbonate: Focus biocatalysis, Biocatalysis and Biotransformation (2023) 1-22.

DOI: 10.1080/10242422.2023.2232914

[17] K. Jagadeeswaraiah et al., The role of tungsten oxide species supported on titania catalysts for the synthesis of glycerol carbonate from glycerol and urea, Catalysis Letters 146 (2016) 692-700.

DOI: 10.1007/s10562-016-1694-9

[18] D. Procopio et al,. An Overview of the Latest Advances in the Catalytic Synthesis of Glycerol Carbonate, Catalysts 12(2022) 50.

DOI: 10.3390/catal12010050

[19] A.A. Babadi et al., Emerging technologies for biodiesel production: processes, challenges, and opportunities, Biomass and Bioenergy 163 (2022): 106521.

DOI: 10.1016/j.biombioe.2022.106521

[20] R. Calmanti et al., High-temperature batch and continuous-flow transesterification of alkyl and enol esters with glycerol and its acetal derivatives, ACS Sustain. Chem. Eng. 6(2018) 3964–3973.

DOI: 10.1021/acssuschemeng.7b04297

[21] P.J.M. Lima et al., An overview on the conversion of glycerol to value‐added industrial products via chemical and biochemical routes, Biotechnology and Applied Biochemistry 69(2022) 2794-2818.

DOI: 10.1002/bab.2098

[22] A. Kaur et al., Lithium zirconate as a selective and cost-effective mixed metal oxide catalyst for glycerol carbonate production, Ind. Eng. Chem. Res. 59(2020) 2667–279.

DOI: 10.1021/acs.iecr.9b05747

[23] S. Arora et al., Valorization of glycerol into glycerol carbonate using the stable heterogeneous catalyst of Li/MCM-41, Journal of Cleaner Production 295(2021) 126437.

DOI: 10.1016/j.jclepro.2021.126437

[24] R. Sedghi et al., Turning biodiesel glycerol into oxygenated fuel additives and their effects on the behavior of internal combustion engines: A comprehensive systematic review, Renewable and Sustainable Energy Reviews 167(2022) 112805.

DOI: 10.1016/j.rser.2022.112805

[25] W. Praikaew et al., Synthesis of Glycerol Carbonate from Dimethyl Carbonate and Glycerol Using CaO Derived from Eggshells, MATEC Web. Conf. 192(2018) 3045.

DOI: 10.1051/matecconf/201819203045

[26] S. Wang et al., Disposable baby diapers waste derived catalyst for synthesizing glycerol carbonate by the transesterification of glycerol with dimethyl carbonate, J. Clean. Prod. 211(2019) 330–341.

DOI: 10.1016/j.jclepro.2018.11.196

[27] S.E. Kondawar et al., Tandem synthesis of glycidol via transesterification of glycerol with DMC over base-mixed metal oxide catalysts, ACS Sustain. Chem. Eng. 5(2017) 1763–1774.

DOI: 10.1021/acssuschemeng.6b02520

[28] R. Dhabhai et al., Purification of glycerol and its conversion to value-added chemicals: A review, Separation Science and Technology 58(2023) 1383-1402.

DOI: 10.1080/01496395.2023.2189054

[29] X. Song et al., High-efficiency and low-cost Li/ZnO catalysts for synthesis of glycerol carbonate from glycerol transesterification: the role of Li and ZnO interaction, Appl. Catal. Gen. 53(2017) 277–85.

DOI: 10.1016/j.apcata.2016.12.019

[30] F.S.H. Simanjuntak et al., Synthesis of glycerol carbonate from glycerol and dimethyl carbonate using magnesium-lanthanum mixed oxide catalyst, Chem. Eng. Sci. 94(2013) 265–270.

DOI: 10.1016/j.ces.2013.01.070

[31] R. Bai et al., Synthesis of glycerol carbonate from glycerol and dimethyl carbonate catalyzed by NaOH/γ-Al2O3, Fuel Proc. Technol. 106(2013) 209–214.

DOI: 10.1016/j.fuproc.2012.07.027

[32] K. Hu et al., KNO3/CaO as cost-effective heterogeneous catalyst for the synthesis of glycerol carbonate from glycerol and dimethyl carbonate, J. Ind. Eng. Chem. 28(2015) 334–343.

DOI: 10.1016/j.jiec.2015.03.012

[33] R. Bai et al., Synthesis of glycerol carbonate from glycerol and dimethyl carbonate catalyzed by KF modified hydroxyapatite, J. Ind. Eng. Chem. 17(2011) 777-781.

DOI: 10.1016/j.jiec.2011.05.027

[34] G. Parameswaram et al., Transesterification of glycerol with dimethyl carbonate for the synthesis of glycerol carbonate over Mg/Zr/Sr mixed oxide base catalysts. Catal. Sci. Technol. 3(2013) 3242–3249.

DOI: 10.1039/c3cy00532a

[35] D. Singh et al., Zinc/lanthanum mixed-oxide catalyst for the synthesis of glycerol carbonate by transesterification of glycerol, Ind. Eng. Chem. Res. 53(2014) 18786–18795.

DOI: 10.1021/ie5011564

[36] J. Poolwong et al., Transesterification of dimethyl carbonate with glycerol by perovskite-based mixed metal oxide nanoparticles for the atom- efficient production of glycerol carbonate, J. Ind. Eng. Chem. 104(2021) 43–60.

DOI: 10.1016/j.jiec.2021.08.008

[37] K. Upendar et al., Low-temperature CO2 adsorption on alkali metal titanate nanotubes, Inter. J. Greenhouse Gas Control. 10(2012) 191-198.

DOI: 10.1016/j.ijggc.2012.06.008

[38] P. Liu et al.,. General Synthesis of glycerol carbonate by transesterification of glycerol with dimethyl carbonate over MgAl mixed oxide catalysts. Applied Catal A, Gen 467(2013)124-131.

DOI: 10.1016/j.apcata.2013.07.020

[39] S. Sandesh et al., Transesterification of glycerol to glycerol carbonate using KF/Al 2O3 catalyst: the role of support and basicity. Catal. Lett. 143(2013) 1226–134.

DOI: 10.1007/s10562-013-1043-1

[40] H. Dehua et al., Catalytic synthesis of glycerol carbonate from biomass-based glycerol and dimethyl carbonate over Li-La2O3 catalysts, Applied Catalysis A: General 564 (2018) 234-242.

DOI: 10.1016/j.apcata.2018.07.032

[41] P. Devi et al. Production of glycerol carbonate using a novel Ti- SBA-15 catalyst. Chem. Eng. J346(2018) 477–488.

DOI: 10.1016/j.cej.2018.04.030

[42] W. Dong et al., Ordered mesoporous BaCO3/C-catalyzed synthesis of glycerol carbonate from glycerol and dimethyl carbonate, Science China Chemistry 58 (2015) 708-715.

DOI: 10.1007/s11426-014-5173-0

[43] M. Malyaadri et al., Synthesis of glycerol carbonate by transesterification of glycerol with dimethyl carbonate over Mg/Al/Zr catalysts. Applied Catal A, Gen 401(2011) 153–157.

DOI: 10.1016/j.apcata.2011.05.011

[44] G. Parameswaram et al., Transesterification of glycerol with dimethyl carbonate for the synthesis of glycerol carbonate over Mg/Zr/Sr mixed oxide base catalysts. Catal Sci Technol 3(2013) 3242–3249.

DOI: 10.1039/c3cy00532a

[45] G. Reyes et al., Effect of the preparation conditions on the catalytic activity of calcined Ca/Al-layered double hydroxides for the synthesis of glycerol carbonate, Applied Catalysis A: General 536 (2017) 9-17.

DOI: 10.1016/j.apcata.2017.02.013

[46] G. Pradhan et al., A greener and cheaper approach towards synthesis of glycerol carbonate from bio waste glycerol using CaO–TiO2 nano catalysts. Journal of Cleaner Production 315 (2021) 127860.

DOI: 10.1016/j.jclepro.2021.127860