The main advantages and disadvantages of solid-phase catalysts for transesterification reactions of oils with alcohols are analyzed. Tests of the sulfonated and phosphated solid - phase catalysts synthesized by us in the transesterification reaction of rapeseed oil with 96% ethanol in order to obtain biodiesel were carried out. The chemical resistance of sulfonated synthetic (S-SCS) and synthesized from natural raw materials (S-KAU) catalysts was compared. The reasons for low chemical resistance of sulfonated carbon-containing materials are determined. Synthetic S-SCS catalysts proved to be the least stable. Regeneration of phosphated samples was performed by washing the catalyst from oil residues and reaction products in a boiling solution of 0.1 M alkali, followed by repeated washing with distilled water to slightly alkaline pH. Then, after drying, the obtained material was used as a source for re-synthesis of the catalyst. The ethanolysis reaction was carried out in autoclaves under pressure at a temperature of 150-160oC with a process duration of 5-7 hours. The ratio of catalyst to starting oil was chosen 1:15 (g : ml). The oil-alcohol ratio was 3: 4, vol. The volume of the autoclave was 45 ml. The maximum conversion under these test conditions in the first cycle for sulfonated catalysts was 100%, and for phosphated - 94%. A carbon-containing catalyst on a ceramic support has been developed, which can be regenerated by firing the carbon-containing material and applying a new one. This catalyst showed the highest chemical resistance, withstanding 7 cycles, while the conversion fell by 14% (from 89 to 75%). For more efficient use of the catalyst, the scheme of flow-circulation installation of transesterification of oils and fats of biological origin with alcohols was proposed.
Zubenko S. O., Patrylak L. K. Methods of obtaining butyl esters of fatty acids: present and prospects. Catalysis and petrochemistry. 2020. 29. 11-23. [in Ukrainian].
Patrylak L. K., Zubenko S. O., Konovalov S. V. Transesterification of rapeseed oil by butanol over alkaline catalysts. Questions of chemistry and chemical technology. 2018. 5. 125-130. [in Ukrainian].
Patrylak L. K., Zubenko S. O., Konovalov S. V. Comparison of physicochemical and operational properties of biodiesel based on methanol and bioalcohols. Catalysis and petrochemistry. 2018. 27. 1–18. [in Ukrainian].
Zubenko S. O., Patrylak L. K. Transesterification of rapeseed oil by butanol. Catalysis and petrochemistry. 2014. 23. 46-48. [in Ukrainian].
Toda M., Takagaki A., Okamura M., Green chemistry — biodiesel made with sugar catalyst. Nature. 2005. 438. 178-178.
Takagaki A., Toda M., Okamura M., Esterification of higher fatty acids by a novel strong solid acid. Catal. Today. 2006. 116. 157–167.
Hao S.J., Takai K., Kang F.Y., Enoki T., Electronic and magnetic properties of acidadsorbed nanoporous activated carbon fibers. Carbon 2008. 46.110–116.
Liu R., Wang X.Q., Zhao X., Feng P.Y., Sulfonated ordered mesoporous carbon for catalytic preparation of biodiesel. Carbon. 2008. 46. 1664–1669.
Hara M., Yoshida T., Takagaki A., A carbon material as a strong protonic acid. Angew. Chem. Int. Ed. 2004. 43. 2955–2958.
Guan Q., Li Y., Chen Y., Shi Y.,. Gu J, Li B. et al., Sulfonated multi-walled carbon nanotubes for biodiesel production through triglycerides transesterification. RSC Adv. 2017. 7. 7250–7258.
Dawodu F.A., Ayodele O., Xin J., Zhang S., Yan D., Effective conversion of nonedible oil with high free fatty acid into biodiesel by sulphonated carbon catalyst. Appl. Energ. 2014. 114. 819–826
Paulina Rechnia-Gorący, Anna Malaika, Mieczysław Kozłowski. Acidic activated carbons as catalysts of biodiesel formation. Diamond and Related Materials. 2018. 87. 124-133.
Kristaps Malins, Valdis Kampars, Janis Brinks, Ilze Neibolte, Raimonds Murnieks. Synthesis of activated carbon based heterogenous acid catalyst for biodiesel preparation. Applied Catalysis B: Environmental. 2015. 176–177. 553-558.
Tamborini L.H., Casco M.E., Militello M.P., Silvestre-Albero J., Barbero C.A., D.F. Acevedo, Sulfonated porous carbon catalysts for biodiesel production: clear effect of the carbon particle size on the catalyst synthesis and properties. Fuel Process. Technol. 2016. 149. 209-217, in: https://doi.org/10.1016/j. fuproc.2016.04.006
Thushari I., Babel S., Sustainable utilization of waste palm oil and sulfonated carbon catalyst derived from coconut meal residue for biodiesel production. Bioresour. Technol. 2018. 248. 199-203.
Strelko V.V., Zazhigalov V.A., Stavitskaya S.S. and other. Selective sorption and catalysis on active carbons. Kyiv: Nauk.dumka, 2008. [in Russian].
Strelko V.V., Stavitskaya S.S., Gorlov Yu. I. Proton catalysis with activatied carbon and partially pyrolized carbonaceous materials. Chinese J. of Catalysis. 2014. 35. 815- 823
Stavitskaya S.S. Catalytic properties of activated carbons. Saarbrucken: Lambert Academic Pablishing, 2012. [in Russian].
Fedorishin A.S., Stavitskaya S.S., Goba V.E. Liquid-phase hydrolysis of ethyl acetate on coals of various origins with different degrees of oxidation. Ukrainian chemical journal 2014. 80(11-12). 87-91. [in Russian].
Zong V-H., Duan Z.-O, Lou W.-Y. Creation and investigation of the properties of solid porous acids and bases as catalysts for the processes of modification of oils and fats. Green Chem. 2007. 7. 434-440.
Stavitskaya S.S., Poddubnaya O.I., Tsyba N.N., Puziy A.M. Catalytic properties of phosphorus-containing carbons in the reaction of hydrolysis of ethyl acetate. Theoretical and experimental chemistry. 2014. 50(3). 185-190. [in Russian].
Stavitskaya S.S., Fedorishin A.S. Catalytic properties of modified carbons in model reactions of synthesis and hydrolysis of esters as a test method for finding effective catalysts for the synthesis of biodiesel fuel. Catalysis and petrochemistry. 2014. 23. 168-173. [in Russian].
Stavitskaya S.S., Puziy A.M., Vikarchuk V.M., Poddubnaya O.I., Tsyba N.N. Structural and sorption properties of active carbons from coconut modified with phosphorus heteroatoms. Theoretical and experiment. chemistry. 2012. 48(12). 252-256. [in Russian].
Puziy A.M., Stavitskaya S.S., Vikarchuk V.M., Poddubnaya O.I., Volynets V.V., Tsyba N.N. Phosphorus-containing activated carbons from coconut, their production and structural-sorption properties. Ukrainian chemical journal 2014. 80(1/2). 93-99. [in Russian].
Stavitskaya S.S., Vikarchuk V.M. , Kovtun M.F., Poddubnaya O.I., Puziy A.M. Adsorption of copper ions by carbon adsorbents modified with phosphoric acid at various temperatures. Chemistry and technol. Water. 2014. 36(2). 203-210. [in Russian].
Stavitskaya S.S., Fedorishin A.S., Strelko V.V. Transesterification and esterification of triglycerides for improving their properties on carbon catalysts. Ukr. chem. Journal. 2016. 82(1–2). 84–90. [in Russian].
Puziy A.M. Methods for obtaining, structure and physico-chemical properties of phosphorylated carbon adsorbents. Theoretical and experiment. chemistry. 2011. 47(15). 265-278. [in Russian].
Puziy A.M., J.M.D. Tascon. Adsorption by phosphorus-containing carbons. In: Novel Carbon adsorbents. Editor - J.M.D. Tascon. Amsterdam: Elsevier. 2012. 245-267. ISBN 9780080977447.
Puziy A.M., Poddubnaya O.I., Martinez-Alonso A., Castro Muñiz A., Suárez-García's F., Tascón J.M.D. Oxygen and phosphorus enriched carbons from lignocellulosic material. Carbon. 2007. 45(10). 1941-1950.
Puziy A.M., Poddubnaya O.I., Martinez-Alonso A. Suárez-García F., Tascón J.M.D. Surface chemistry of poshphorus-containing carbons of lignocellulosic origin. Carbon. 2005. 43(14). 2857-2868.
Puziy A.M., Poddubnaya O.I., Ziatdinov A.M. On the chemical structure of poshphorus compounds in phosphoric acid-activated carbon. Applied Surfce Science. 2006. 252(23). 8036-8038.
Puziy A.M., Poddubnaya O.I., Ritter J A., Ebner A.D., Holland C.E. Elucidation of the ion dinding mechanism in heterogeneous carbon-composite adsorbents. Carbon. 2001. 39(15). 2313-2324.
Puziy A.M., Poddubnaya O.I., Sobiesiak M. Gawdzik В. Structural and sulface heterogeneity of phosphorus-containing polyimide-derived carbons: effect of heat treatment temperature. Adsorption. 2013. 19(2-4). 717-722.
Gryglewicz S. Rapeseed oil methyl esters preparation using heterogeneous catalysts. Bioresource Technology. 1999. 70(3). 249–253.
Tarkovskaya I.A. Oxidized carbons. Kiev: Nauk.dumka, 1981. 198 p. [in Russian].
Riemann W., Walton G., Ion exchange chromatography in analytical chemistry. M.: Mir. 1973. 393 p. [in Russian].
Fedorishin A. S., Strelko V. V., Stavitskaya S. S., Yakovlev V. I., Tsyba N. N., Mil’grandt V. G. Solid Acid Catalysts for Synthesis of Biodiesel Fuel from Pyrolyzed Natural and Synthetic Polymeric Materials Russian Journal of Applied Chemistry, 2010. 83(2). 281−286.
Fedoryshyn O.S., Romanova I.V., Catalytic properties of P and S-containing acid carbon materials in the transesterification reaction of rapeseed oil with ethanol. Theoretically. and experiment. chemistry. 2021. 57(2). 121-125. [in Ukrainian].
Fedorishin A.S., Stavitskaya S.S. Search for new carbon catalysts for the synthesis of biofuels from plant materials. Ukrainian chemical journal. 2018. 84(6). 84-90. [in Russian].
Pat. 109799. Ukraine. Denisovich V.O., Shirokov D.O., Fedoryshyn O.S., Bondar R.V., Strelko V.V., Installation for transesterification of vegetable oils and / or fats of biological origin. 2015 [in Ukrainian].
Kafarov V.V., Fundamentals of mass transfer. Emulsifying columns, Moscow: Higher school, 1972, p. 434-437. [in Russian].
Pat. US2009076985A1; WO2009038864A1, Morgan William Douglas. Method for obtaining biodiesel, alternative fuels and renewable fuels tax credits and treatment. 2009.
Pat. ЕР 2348009, EP2348009A2. Cho Hyun-Jun, Ham Byoung-Kyung, Kim Soo-Hyun, Lim Jae-Bong, Moon Chan-Woo. Method and apparatus for preparing alkyl ester fatty acid using fatty acid .2011.
Pat. ЕР 2457648 А1. Dimian Alexandre, Rothenberg Gadi, Schut Ronald. Production of fatty acid alkyl esters. 2012.
Pat. EP2154226A1; WO2010010111A1. Dimian Alexandre. Rothenberg Gadi. Process for manufacturing acid esters through reactive distillation. 2010.
Patent 101360. Ukraine. Strelko V.V., Denisovich V.O., Fedorishin O.S., Shirokov D.O., Mironyuk T.I. Method of transesterification with alcohols of oils and / or fats of biological origin. 2013. [in Ukrainian].