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(II)-Exchanged Heteropolyacids on Silica As Catalysts for Acid-Catalyzed Esterification Reactions

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(II)-Exchanged Heteropolyacids on Silica As Catalysts for Acid-Catalyzed Esterification Reactions https://doi.org/10.3311/PPch.14788 Creative Commons Attribution b |21 Periodica Polytechnica Chemical Engineering, 65(1), pp. 21–27, 2021 Immobilizing Ni (II)-Exchanged Heteropolyacids on Silica as Catalysts for Acid-Catalyzed Esterification Reactions Qiuyun Zhang1,2*, Dandan Lei1, Qianqian Luo1, Taoli Deng1, Jingsong Cheng1, Yutao Zhang2, Peihua Ma3** 1 School of Chemistry and Chemical Engineering, Anshun University, Anshun 561000, Guizhou Province, China 2 Engineering Technology Center of Control and Remediation of Soil Contamination of Provincial Science & Technology Bureau, Anshun University, Anshun 561000, Guizhou Province, China 3 School of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, Guizhou Province, China * First corresponding author, e-mail: [email protected]; ** Second corresponding author, e-mail: [email protected] Received: 03 August 2019, Accepted: 30 October 2019, Published online: 28 November 2019 Abstract Biodiesel was synthesized from oleic acid using Ni (II)-exchanged heteropolyacids immobilized on silica ( Ni0.5H3SiW / SiO2 ) as a solid acid catalyst. Based on detailed analyses of FT-IR, XRD, TG and SEM, the structural, surface and thermal stability of Ni0.5H3SiW / SiO2 were investigated. Obtained results demonstrated that the Keggin structure was well in the immobilization process and possess a high thermal stability. Various esterification reaction conditions and reusability of catalyst were studied. High oleic acid conversion of 81.4 % was observed at a 1:22 mole ratio (oleic acid: methanol), 3 wt. % catalyst at 70 °C for 4 h. The Ni0.5H3SiW / SiO2 catalyst was reused for several times and presented relatively stable. More interestingly, the kinetic studies revealed the esterification process was compatible with the first order model, and a lower activation energy was obtained in this catalytic system. Keywords heteropolyacids, Ni salts of silicotungstic acid, SiO2 , esterification, biodiesel 1 Introduction In recent years, the threats of fossil resource exhaus- the formation of soap [8]. To overcome these problems, tion and worldwide environmental problems are becom- the esterification for high acid value oils have been per- ing more serious [1-3]. In this context, the production of formed using acid catalysts. Unfortunately, this homoge- biodiesel is considered to have particularly high potential neous acid catalysts are corrosive, difficult to recycle, and alternative fuel to conventional fossil diesel. Additionally, produce large amounts of waste water [9, 10]. As solid biodiesel is superior to fossil diesel fuel in terms of good acid catalysts can be easily removed from the reaction biodegradability, low toxicity, sulfur content, flash point mixture and avoid producing large amount of wastewater and lubricity characteristics, which prolong engine life [4]. contributing to polluting the environment, which is cur- Generally, Biodiesel (fatty acid methyl esters) is produced rently an active area of research [11]. A variety of solid by esterification or transesterification of free fatty acids acid catalysts are comprehensively reported in literature (FFAs), vegetable oils and animal fats with low molecular and applied to produce biodiesel [12, 13]. weight alcohols, usually methanol or ethanol, in the pres- Amongst several solid acid catalysts developed, ence of an acid/base catalyst [5, 6]. the heteropolyacids have been seen as one of the prom- In the production process, the expense of the raw ising option for use in biodiesel production process, own- materials is the major contributor to the cost of biodiesel ing to its strong Brönsted acidity and high proton mobil- production [7]. Thus, the low-cost oils are an economi- ity [14]. However, high solubility in polar solvents and cal raw material for the production of biodiesel, such as low specific surface area is two major disadvantages that non-edible vegetable oils and waste oils. However, these limit its further application [15]. Because of that, hetero- oils contain large amounts of free fatty acids, which lead polyacids supported are usually more effective for cata- to the deactivation of the alkaline catalysis and even to lytic reactions [16-18]. Hence, in the present work, the Ni Cite this article as: Zhang, Q., Lei, D., Luo, Q., Deng, T., Cheng, J., Zhang, Y., Ma, P. "Immobilizing Ni (II)-Exchanged Heteropolyacids on Silica as Catalysts for Acid-Catalyzed Esterification Reactions", Periodica Polytechnica Chemical Engineering, 65(1), pp. 21–27, 2021.https://doi.org/10.3311/PPch.14788 Zhang et al. 22|Period. Polytech. Chem. Eng., 65(1), pp. 21–27, 2021 (II)-exchanged heteropolyacids immobilized on silica 2.4 Catalytic reaction procedure solid acid catalyst was prepared by a facile synthesis pro- The esterification process was conducted in a three- cess. The synthesized catalyst was characterized by X-ray neck round bottom flask equipped with mechanical stir- diffraction (XRD), scanning electron microscopy (SEM), rer, condenser and thermometer in oil bath to maintain fourier transform infrared spectroscopy (FT-IR), thermo- the reaction temperature. In a typical experimental run, gravimetric analysis (TG), and used as a solid catalyst the desired amount of oleic acid (lauric, myristic, pal- for the biodiesel of production were investigated via ester- mitic or stearic acid) was mixed with the desired amount ification of oleic acid with methanol. Various parameters of catalyst. Then, the required amount of methanol at an such as catalyst dosage, molar ratio, temperature, time and appropriate ratio was added, and the reaction mixture was reusability of catalyst were examined. Furthermore, the heated at different temperature (20-70 °C) for a desired kinetics and activation energy for the as-prepared cata- period of time. After the reaction, the catalysts were sep- lyzed esterification were also assessed. arated from the solution by filtration, and water and meth- anol were removed with a rotary evaporator. The conver- 2 Materials and methods sion of oleic acid (lauric, myristic, palmitic or stearic acid) 2.1 Materials could be derived from Eq. (1) [19]: Silicotungstic acid (H4SiW, H4SiW12O40 · nH2O), nickel (II) Conversion % 1 100 % ()=−()αα12× , (1) nitrate hexahydrate (AR), silica ( SiO2 ), oleic acid (AR), lauric acid (AR, 98 %), stearic acid (AR, 98 %), myristic where α1 represents the acid value of raw materials, α2 rep- acid (AR, 98 %), palmitic acid (AR, 98 %) was purchased resents the acid value of esterification product. The acid from Shanghai Aladdin Industrial Inc. All chemicals were value was determined by ISO 660–2009 standard [20]. used without further purification, unless otherwise noted. 3 Results and discussion 2.2 Preparation of the catalysts 3.1 Catalyst characterization The SiO2 was used as a support for the preparation The FT-IR spectrum of H4SiW, Ni 0.5H3SiW, SiO2 and of Ni0.5H3SiW / SiO2 catalyst. In the typical synthesis, Ni0.5H3SiW / SiO2 was given in Fig. 1 (a). As can be seen the required quantity of H4SiW (1440 mg) as dissolved Fig. 1 (a), the FT-IR curve of H4SiW, Ni 0.5H3SiW and in 5 ml of deionized water, nickel (II) nitrate (70 mg) aqueous Ni0.5H3SiW / SiO2 exhibit four strong peaks at 980, 927, −1 solution was added dropwise into the H4SiW aqueous solu- 884 and 804 cm , which represent the stretching vibra- tion, and kept stirring for over 3 h in oil bath with 70-80 °C. tions of W=O, Si–O, W–Oc–W, and W–Oe–W, respec- Subsequently, the desired amount of SiO2 (2420 mg) was tively [21], and show the existence of the Keggin struc- used in the above solution and continue stirred for 1 h, and tures. This indicated that the Keggin structure of H4SiW the obtained solid products were then filtered, washed and was still good in the immobilization process. In addi- dried in an oven at 120 °C for 12 h. These as-prepared cat- tion, compared with pure SiO2 , Ni0.5H3SiW / SiO2 exhibits alyst is denoted as Ni0.5H3SiW / SiO2. For the comparison, the similar diffraction peaks. The FT-IR spectral results using the above procedure, the Ni0.5H3SiW sample was also suggested that the Ni0.5H3SiW has been successfully immo- synthetized. Prior to use, the obtained Ni0.5H3SiW / SiO2 cat- bilized on the surface of SiO2 . The XRD pattern was used alyst was dried at 120 °C. to confirm the structure of Ni0.5H3SiW / SiO2 (Fig. 1 (b)). Compared with H4SiW and Ni0.5H3SiW, Ni 0.5H3SiW / SiO2 2.3 Characterization also shows the similar diffraction peaks at 8.0°, 20.9°, XRD spectra were obtained using a D8 Advance equip- 36.6°, 45.9° and 60.1° with some deviation. This may be ment using graphite monochromator and monochro- due to the Ni0.5H3SiW / SiO2 composite has an interaction matic CuKα radiation (1.5406 Å). FT-IR analyses were between Ni0.5H3SiW and SiO2 . Based on these results, obtained using a PerkinElmer spectrum100 using the KBr this assures that Ni0.5H3SiW are immobilized on the sup- disc technique (4000-400 cm−1). TG has performed on a ported surface successfully. Fig. 1 (c) shows the TG result NETZSCH/STA 409 PC Luxx simultaneous thermal ana- of Ni0.5H3SiW / SiO2 . The slight weight loss before 200 °C is lyzer with a heating rate of 5 °C / min under an air flow assignable to the loss of residual solvent or water. No major rate of 20 mL / min. SEM images were conducted using weight loss occurred above 200 °C for the composite mate- a Hitachi S4800 scanning electron microscope. rials, suggesting a considerably high thermal stability. Zhang et al. Period. Polytech. Chem. Eng., 65(1), pp. 21–27, 2021| 23 Fig. 2 The SEM image of (a) H SiW, (b) Ni H SiW, and Fig. 1 (a) FT-IR spectra of H4SiW, Ni 0.5H3SiW, SiO2 and 4 0.5 3 (c) Ni H SiW/SiO . Ni0.5H3SiW / SiO2 (b) XRD patterns of H4SiW, Ni 0.5H3SiW and 0.5 3 2 Ni0.5H3SiW / SiO2 ; (c) TG curve of Ni0.5H3SiW / SiO2 . SEM images of the H4SiW, Ni 0.5H3SiW and 3.2 The catalytic activity of Ni0.5H3SiW / SiO2 Ni0.5H3SiW / SiO2 samples are shown in Fig.
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