In this work, synthesis of several types of calcium oxide based catalysts by mechanochemical treatment and subsequent calcination is presented. Prepared nanocomposite CaO·ZnO, calcium containing perovskites CaTiO3, CaMnO3, CaZrO3 and Ca2Fe2O5, a series of CaO·SiO2 mixed oxides and calcium diglyceroxide (CaDG) were characterized and tested in the methanolysis of sunflower oil under different working conditions: catalyst amount, agitation speed, temperature and methanol to oil molar ratio

Kesić, Željka

Lukić, Ivana

Skala, Dejan

Zdujić, Miodrag

English

Serbian Academy of Science and Arts Digital Archive (DAIS)

       PHYSICAL CHEMISTRY 2018  14th International Conference on Fundamental and Applied Aspects of Physical Chemistry    Proceedings Volume I              September 24-28, 2018  Belgrade, Serbia   II  ISBN 978-86-82475-36-1 Title: Physical Chemistry 2018 (Proceedings)Editors: Željko Čupić and Slobodan Anić Published by: Society of Physical Chemists of Serbia, Studentski Trg 12-16, 11158, Belgrade, Serbia Publisher: Society of Physical Chemists of Serbia For Publisher: S. Anić, President of Society of Physical Chemists of Serbia Printed by: ʺJovanʺ, <Printing and Publishing Company, 200 Copies Number og pages: 550+6, Format B5, printing finished in September 2018 Text and Layout: ʺJovanʺ  Neither this book nor any part may be reproduced or transmitted in any form or by any means, including photocopying, or by any information storage and retrieval system, without permission in writing from the publisher.          200 - Copy printing                         III         CONTENT    Volume I  Organizer IV Comittes V Sponsors VI Plenary Lecture 1 Chemical Thermodynamics 57 Spectroscopy, Molecular Structure, Physical Chemistry of Plasma 71 Kinetics, Catalysis  157 Nonlinear Dynamics, Oscillatory Reactions, Chaos 253 Electrochemistry  361 Biophysical Chemistry, EPR investigations of biosystems, Photochemistry, Radiation Chemistry 419       IV       PHYSICAL CHEMISTRY 2018  14th International Conference on  Fundamental and Applied Aspects of Physical Chemistry     Organized by  The Society of Physical Chemists of Serbia  in co-operation with  Institute of Catalysis Bulgarian Academy of Sciences  and  Boreskov Institute of Catalysis Siberian Branch of   Russian Academy of Sciences  and  University of Belgrade, Serbia:  Faculty of Physical Chemistry Institute of Chemistry, Technology and Metallurgy Vinča Institute of Nuclear Sciences Faculty of Pharmacy Institute of General and Physical Chemistry, Belgrade, Serbia     V Organizing Committee  Chairman:   S. Anić (Serbia)  Vice-chairmans:  M. Gabrovska (Bulgaria) A. A. Vedyagin (Russia) S. N. Blagojević (Serbia)  Members: N. Cvjetičanin (Serbia), S. M. Blagojević (Serbia), M. Daković (Serbia), J. Dimitrić-Marković (Serbia), T. Grozdić (Serbia), Lj. Ignjatović (Serbia), D. Jovanović (Serbia),J. Jovanović (Serbia), M. Kuzmanović (Serbia), D. Marković (Serbia), B. Milosavljević (USA), M. Mojović (Serbia), N. Ostrovski (Serbia), N. Pejić (Serbia), M. Petković (Serbia), A. Popović-Bjelić (Serbia), B. Simonović (Serbia), D. Stanisavljev (Serbia), M. Stanković (Serbia), Z. Šaponjić (Serbia), B. Šljukić (Serbia), G. Tasić (Serbia), S. Veličković (Serbia), N. Vukelić (Serbia)  Scientific Committee  Chairman:   Ž. Čupić (Serbia) Vice-chairmans:  V. Bukhtiyarov (Russia)  S. Todorova (Bulgaria)  B. Adnađević (Serbia)  Members: S. Anić (Serbia), A. Antić-Jovanović (Serbia), D. J. Biswas (India), R. Cervellati (Italy), G. Ćirić-Marjanović (Serbia), V. Dondur (Serbia), S. D. Furrow (USA), A. Goldbeter (Belgium), R. Jerala (Slovenia), M. Jeremić (Serbia), A. Jovović (Serbia), Y. Kalvachev (Bulgaria), E. Kiš (Serbia), Lj. Kolar-Anić (Serbia), U. Kortz (Germany), T. Kowalska (Poljska), V. Kuntić (Serbia), G. Lente (Hungary), Z. Marković (Serbia), S. Mentus (Serbia), K. Novaković (UK), B. Novakovski (Poljska), S. Otto  (Netherlands), V. Parmon (Russia), R. Pascal (USA), M. Perić (Serbia), M. Plavšić (Serbia), J. Savović (Serbia), G. Schmitz (Belgium), I. Schreiber (Czech), L. Schreiberova (Czech), H. W. Siesler (Germany), E. M. Barbosa Souto (Portugal), N. Stepanov (Russia), E. Szabó (Slovakia), R. Tomovska (Spain), Á. Tóth (Hungary), M. Trtica (Serbia), V. Vasić (Serbia), D. Veselinović (Serbia), D. Vučković (Canada),  V. Vukojević (Sweden), P. Walde (Switzerland)  Local Executive Committee  Chairman:   S.N. Blagojević Vice-chairmans:  A. Ivanović-Šašić A. Stanojević  Members: M. Ajduković, I. N. Bubanja, A. Dobrota, J. Dostanić, D. Dimić, A. Ignjatović, S. Jovanović, Z. Jovanović, A. Jović, N. Jović-Jovičić, D. Lončarević, M. Kragović, J. Krstić, S. Maćešić, J. Maksimović, S. Marinović, V. Marković, D. Milenković, M. Milovanović, T. Mudrinić, B. Nedić, M. Pagnacco, A. Pavićević, N. Potkonjak, D. Ranković, M. Ristić,  B. Stanković, K. Stevanović,  M. Stević,  A. Stoiljković          PHYSICAL CHEMISTRY 2018    C-06-O   193 SYNTHESIS OF CALCIUM OXIDE BASED CATALYSTS FOR BIODIESEL PRODUCTION  I. Lukić1*, Ž. Kesić1, M. Zdujić2 and D. Skala1  1 University of Belgrade, Faculty of Technology and Metallurgy, Karnegijeva 4, 11000 Belgrade, Serbia. (ivanal888@yahoo.co.uk) 2Institute of Technical Sciences of SASA, KnezMihailova 35, 11000 Belgrade, Serbia.   ABSTRACT In this work, synthesis of several types of calcium oxide based catalysts by mechanochemical treatment and subsequent calcination is presented. Prepared nanocomposite CaO·ZnO, calcium containing perovskites CaTiO3, CaMnO3, CaZrO3 and Ca2Fe2O5, a series of CaO·SiO2 mixed oxides and calcium diglyceroxide (CaDG) were characterized and tested in the methanolysis of sunflower oil under different working conditions: catalyst amount, agitation speed, temperature and methanol to oil molar ratio.   INTRODUCTION Biodiesel, a mixture of fatty acid methyl esters (FAME), due to its environmental benefits such as non-toxicity and biodegradability and the fact that it might be synthesized from renewable resources, has gained significant attention as a promising alternative substitute to diesel fuels. Commonly, biodiesel is produced by alcoholysis of different triacylglycerols in the presence of homogeneous or heterogeneous catalysts. Calcium oxide due to the high activity, availability and low cost is one of the most studied heterogeneous catalysts [1]. However, since leaching into the reaction medium was observed for this catalyst, it is important to improve CaO properties by supporting it on different carriers or mixing with other oxides. Mechanochemical synthesis is a simple and waste-free technique for the preparation of different materials, including catalysts.  Milling of CaO and ZnO with water was carried out to obtain calcium zinc hydroxide hydrate (CaZn2(OH)6·2H2O), which was subsequently transformed to CaO·ZnO catalyst by calcination at 700 °C for 3h [2]. Calcium diglyceroxide (Ca(C3H7O3)2) was synthesized by mechanochemical treatment of CaO dispersed in glycerol [3]. Calcium-containing perovskites CaTiO3, CaMnO3, CaZrO3 and Ca2Fe2O5 were synthesized by calcination of mechanochemically treated stoichiometric mixtures of CaCO3 and either TiO2, MnO2, ZrO2 or Fe2O3 powders [4]. Mixtures of CaO and SiO2 in a molar        PHYSICAL CHEMISTRY 2018    C-06-O   194 ratio in the range of 1 to 3 with addition of water have been mechanochemically treated and calcined to prepare a series of CaO·SiO2 mixed oxides.   EXPERIMENTAL Mechanochemical treatment of different starting materials was carried out in the planetary ball mill Fritsch Pulverisette 5, in air atmosphere. The prepared catalysts were characterized by XRD, TGA/DSC, FTIR, SEM/EDX, and base strength using Hammett indicator method. The detailed preparation of catalysts and the used instruments for their characterization are described elsewhere [2-4]. The methanolysis of sunflower was carried out in 300 cm3 batch autoclave or in a 250 ml three-necked thermostated glass flask with a condenser and magnetic stirrer under different working conditions: catalyst amount, agitation speed, temperature and methanol to oil molar ratio.   RESULTS AND DISCUSSION The X-ray diffraction patterns of prepared catalysts are shown in Fig. 1.  Figure 1. XRD patterns of synthesized catalysts  Mechanochemical treatment of CaO and ZnO powder mixture with water and subsequent calcination led to the formation of fine composite powder composed of CaO and ZnO. The formation of CaDG by mechanochemical        PHYSICAL CHEMISTRY 2018    C-06-O   195 treatment of CaO and glycerol was confirmed with all the peaks well indexed to the calcium diglyceroxide phase Ca(C3H7O3)2. XRD patterns revealed that CaTiO3, CaMnO3, CaZrO3 and Ca2Fe2O5 perovskites consist dominantly of one phase. Milling of CaO + SiO2 powder mixtures with molar ratio in the range of 1–2 followed by calcination at 900 °C for 48 h, produced single-phase calcium silicate compounds, while starting from the 3CaO + SiO2 powder mixture, two phase CaO/Ca2SiO4 was obtained.    Table 1. Catalytic activity of synthesized catalysts Catalyst Starting material and calcination temperature Basic strength Reaction conditionsa FAME yield, % CaO·ZnO CaO + ZnO + H2O  Tcalc=700 °C, 3h 11<H_<18.4 T = 60 °C;  MR = 10:1;  Cat = 2%;  t = 4h 98.2 Ca(C3H7O3)2 (CaDG) CaO + Glycerol  / 11<H_<15.0 T = 60 °C;  MR = 10:1;  Cat = 0.5%;  t = 2h 97.9 CaTiO3 CaZrO3 CaMnO3 Ca2Fe2O5  bCaO/CaTiO3 CaCO3 + TiO2 CaCO3 + ZrO2 CaCO3 + MnO2 CaCO3 + Fe2O3 Tcalc=700 °C; 24 bCaCO3 + TiO2 Tcalc=1050 °C,2 h 6.8 <H_< 9.3 6.8 <H_< 9.3 6.8 <H_< 9.3 6.8 <H_< 9.3  b9.3 <H_< 10 T = 60 °C;  MR = 6:1;  Cat = 10%;  t = 10h 0.1 0.0 0.0 0.0  b98.1 CaSiO3 Ca3Si2O7 Ca2SiO4 CaO/Ca2SiO4 CaO + SiO2 3CaO + 2SiO2 2CaO + SiO2 3CaO + SiO2 Tcalc =900 °C,48h H_< 9.3 H_< 9.3 H_< 9.3 11<H_<15 T = 60 °C;  MR = 10:1;  Cat = 2%;  t = 5h 0.31 0.52 0.81 96.03 aT = temperature; MR = molar ratio methanol to oil; Cat = catalyst loading; t = time. bMixed using agate mortar and pestle (but without subsequent mechanochemical treatment)           PHYSICAL CHEMISTRY 2018    C-06-O   196 The results of catalytic activity of the prepared catalysts in methanolysis of sunflower oil, along with their basic strength (H_), reaction conditions, and preparation procedure are given in Table 1. The high FAME yields were achieved when CaO·ZnO and CaDG were used as catalysts, as well as two-phase samples containing CaO, while pure perovskites and calcium silicates showed no activity in methanolysis at 60 °C. High catalytic activity of prepared catalysts is related to high basic strength, which is considered as one of the most significant factor that affects the activity of different catalysts for biodiesel production. With the exception of CaDG, which has different structure, in all other cases the high basicity of samples, accompanied with their high catalytic activities, arises from the existence of CaO phase. The perovskites possess different structure compared to the rock salt structure of CaO and from that reason they are not active in transesterification of sunflower oil at lower temperature.   CONCLUSION Mechanochemical treatment was successfully used for the synthesis of various CaO based heterogeneous catalysts. Prepared CaO·ZnO and CaDG showed a high catalytic activity in methanolysis of sunflower oil at 60 °C resulting in FAME yield over 96%. Under these conditions, pure perovskites (CaTiO3, MnO3, CaZrO3 and Ca2Fe2O5) and pure calcium silicates (CaSiO3, Ca3Si2O7 and Ca2SiO4) phases exhibited no catalytic activity, while two-phase samples containing CaO (CaTiO3/CaO and Ca2SiO4/CaO) were active.  Acknowledgement  This work was financially supported by the Ministry of Education, Science and Technological Development of the Republic of Serbia (III 45001).  REFERENCES [1] Ž. Kesić, I. Lukić, M. Zdujić, Lj. Mojović, D. Skala, Chemical Industry and Chemical Engineering Quarterly, 2016, 22, 391−408. [2] Ž. Kesić, I. Lukić, D. Brkić, J. Rogan, M. Zdujić, H. Liu, D. Skala, Applied Catalysis A: General, 2012, 427–428, 58–65. [3] I. Lukić, Ž. Kesić, M. Zdujić, D. Skala, Fuel, 2016, 165, 159–165. [4] Ž. Kesić, I. Lukić, M. Zdujić, Č. Jovalekić, V. Veljković, D. Skala, Fuel Processing Technology, 2016, 143, 162–168. 

Synthesis of calcium oxide based catalysts for biodiesel production

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Synthesis of calcium oxide based catalysts for biodiesel production

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