Glycerol acetins: fuel additive synthesis by acetylation and esterification of glycerol using cesium phosphotungstate catalyst

Sandesh, Swetha; Manjunathan, Pandian; Halgeri, A. B.; Shanbhag, Ganapati V.

doi:10.1039/c5ra17623a

Cited by 57 publications

(41 citation statements)

References 37 publications

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“…The protonated acetic acid is then attacked by the oxygen of glycerol, forming monoacetin with the loss of one water molecule. The monoacetin formed gives diacetin and triacetin in a series reaction (Sandesh et al, 2015). % was achieved at the glycerol/acetic acid ratio of 1:10.…”

Section: Effect Of Reactants Molar Ratiomentioning

confidence: 95%

Kinetic studies on the synthesis of fuel additives from glycerol using CeO2–ZrO2 metal oxide catalyst

Kulkarni¹,

Britto²,

Narula³

et al. 2020

Biofuel Res. J.

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Kinetic studies on the synthesis of fuel additives from glycerol using CeO2-ZrO2 metal oxide catalyst. Keywords:Biodiesel Glycerol Fuel additive Acetins Mixed oxide catalyst Kinetic model Highly stable and active CeO2-ZrO2 metal oxide catalyst was synthesized via the combustion method and was further functionalized with sulphate (SO4 2-) groups. The morphology, surface functionalities, and composition of the metal oxide catalyst were determined by scanning electron microscopy, N2 adsorption and desorption measurement, X-ray diffraction, and Fourier transform infrared spectroscopy. The synthesized catalyst was used for esterification of glycerol with acetic acid. Effects of the process parameters including acetic acid to glycerol molar ratios (3-20), catalyst loadings (1-9 wt.%) and reaction temperatures (70-110°C) on the glycerol conversion and glycerol acetates selectivity were studied. Excellent catalytic activity was observed by using the sulphated metal oxide catalyst resulting in a glycerol conversion as high as 99.12%. The selectivity towards the di and triacetin (fuel additive) formed stood at 57.28% and 21.26% respectively. The reaction rate constants and activation energies were also estimated using a Quasi-Newton algorithm, namely Broyden's method and Arrhenius equations at 80-110℃. The calculated values were in accordance with the experimental values which confirmed the model. Finally, the developed catalyst could be reused for three consecutive cycle without major loss of its activity. Overall, the findings presented here could be instrumental to drive future research and commercialization efforts directed toward biodiesel glycerol valorisation into fuel additives.© 2020 BRTeam. All rights reserved.Journal homepage: www.biofueljournal.com HIGHLIGHTS GRAPHICAL ABSTRACT ARTICLE INFO ABSTRACT➢Mixed oxide CeO2-ZrO2 catalyst in unsulphated and sulphated forms was used for glycerol acetylation to produce acetins (fuel additives). ➢Both unsulphated and sulphated mixed oxide catalysts were fully characterized. ➢SO4 2-/CeO2-ZrO2 led to glycerol conversion of 99.12% with selectivity of 57.28% and 21.26% towards di and triacetins, respectively. ➢The activation energy for monoacetin, diacetin, and triacetin formation were 5.34, 16.40, and 43.57 kJ.mol-1, respectively. ➢Regeneration studies indicated the reusability of the catalyst up to three consecutive cycles. Kinetic studies on the synthesis of fuel additives from glycerol using CeO2-ZrO2 metal oxide catalyst.

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Section: Effect Of Reactants Molar Ratiomentioning

confidence: 95%

Kinetic studies on the synthesis of fuel additives from glycerol using CeO2–ZrO2 metal oxide catalyst

Kulkarni¹,

Britto²,

Narula³

et al. 2020

Biofuel Res. J.

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“…The fundamental reaction pathway of esterification of glycerol with acetic acid involves the Fischer esterification mechanism [1,2]. Kale et al and Sandesh and co-workers reported that over ion exchange resins possesing high acidity, the addition of proton to the carbonyl oxygen takes place (Figure 7b), which generates positive charge on the carbonyl carbon and facilites the nucleophilic attack of hydroxyl group from glycerol [8,39]. They also reported that monoacetin is produced and subsequently diacetin and triacetin are observed in the consecutive steps, producing water as a by-product.…”

Section: Influence Of Reaction Conditions: Effect Of the Reaction Timmentioning

confidence: 99%

Binary Oxides with Defined Hierarchy of Pores in the Esterification of Glycerol

et al. 2016

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Abstract:Various porous binary oxides with elevated textural properties were obtained in this work. The as-synthesized solids were calcined or modified by reflux and extraction processes. Characterizations through SEM, nitrogen physisorption and TEM techniques demonstrated the formation of porous metal oxide networks over all solids. XRD, thermal analyses and FTIR measurements showed the existence of nanosized rutile TiO 2 , tetragonal ZrO 2 , SiO 2 and γ-Al 2 O 3 phases on the solids. The structure and texture of the as-synthesized SiAl sol-gel derived solid resulted in the formation of well-dispersed nanoparticles on the support. The removal of the organic compounds by ethanol extraction or reflux from SiAl resulted in the presence of structures with defined hierarchy of pores. Among the solids studied, the catalytic results in the esterification of glycerol with acetic acid indicated that best performances were obtained over SiAl sample when submitted to extraction and reflux treatments. This was due to the creation of accessible pores, which facilitated the reaction occurrence at glycerol to acetic acid molar ratio = 1:3 and T = 80 • C for 20 h using 75 mg of catalyst. The solids can be reused three times without complete loss of their catalytic performance.

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“…This could be explained by the fact that the presence of a higher amount of Brønsted acid sites (A15 catalyst) in reaction mix could augment CA conversion; nevertheless, it has negatively influenced GMC selectivity. 21 Again, electromagnetic energy (UV-visible spectra) contributed by quartz-halogen radiator caused excitation and relocation of electron-hole pairs from the valence band to conduction band in NT-P25, thereby facilitating higher GMC selectivity and CA conversion simultaneously. The individual effect of Ti 4+ and H + ions at lower conversion below 20% could be observed from Figure 2d.…”

Section: Effect Of Catalystmentioning

confidence: 99%

“…However, it could be inferred from Table 3 that increase in Brønsted acidity (H + ) in ATO mixture deteriorated GMC selectivity, which indicated that monoester selectivity was predominantly controlled by Lewis acid catalytic sites. 21 Again, electromagnetic energy (UV-visible spectra) contributed by quartz-halogen radiator caused excitation and relocation of electron-hole pairs from the valence band to conduction band in NT-P25, thereby facilitating higher GMC selectivity and CA conversion simultaneously. 22 Moreover, ATO dosage also played an important role in improving GMC selectivity and CA conversion (Figure 2c).…”

Section: Effect Of Catalystmentioning

confidence: 99%

Quartz halogen‐ultrasonication integrated rotating reactor for efficient photocatalytic‐thermocatalytic synthesis of glyceryl monocaprin: Kinetics of heterogeneous esterification

Karan

Mukhopadhyay

Chakraborty

2019

Asia-Pacific J Chem Eng

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A pioneering intensification protocol for glyceryl monocaprin (GMC) synthesis deploying coactive electromagnetic energies,viz. quartz halogen radiation (QHR) and ultrasonication (US) is explored. Concurrently, Amberlyst 15 (A15) and nano-TiO 2 P25 (NT-P25) were applied to achieve capric acid (CA) conversion of 97% ± 0.5%, employing the integrated QHR-US energized rotating reactor (QHRUERR), which was 7.5% ± 0.5% higher than QH energized rotating reactor (QHERR) and 20% ± 1% greater compared to an ultrasonically energized rotating reactor (USERR). Optimal factors, viz., 0.35:1 CA:glycerol mole ratio, 343K temperature, 0.67:1 A15:P25(wt./wt.) dose, resulted maximum GMC selectivity (95% ± 0.3%). Langmuir-Hinshelwood model (R 2 = .99) could best represent the esterification kinetics in QHRUERR under optimal condition. Significantly, reaction activation energy was found minimum in QHRUERR (9.63 kJ/mol) compared with a rotating reactor equipped either with QHR (27.5 kJ/mol) or the US (32.74 kJ/mol), thus implying promising synergy and energy efficiency of QHRUERR. Ultraviolet-visible diffuse reflectance spectra and photoluminescence analyses exhibited the photoactivity of ATO (A15 : NT-P25=0.67: 1 w/w) catalyst possessing lower band gap energy (2.98 eV). The optimal product GMC demonstrated appreciable food preservative attributes toward Aspergillus Niger food pathogen. An energy-efficient and sustainable reactor could, thus, be explored in this study for proficient green synthesis of valuable food preservatives.

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Glycerol acetins: fuel additive synthesis by acetylation and esterification of glycerol using cesium phosphotungstate catalyst

Abstract: Glycerol acetylation and esterification reactions with acetic anhydride and acetic acid respectively give acetins, in which di and tri acetins are commercially important products used as fuel additives.

Cited by 57 publications

References 37 publications

Kinetic studies on the synthesis of fuel additives from glycerol using CeO2–ZrO2 metal oxide catalyst

Kinetic studies on the synthesis of fuel additives from glycerol using CeO2–ZrO2 metal oxide catalyst

Binary Oxides with Defined Hierarchy of Pores in the Esterification of Glycerol

Quartz halogen‐ultrasonication integrated rotating reactor for efficient photocatalytic‐thermocatalytic synthesis of glyceryl monocaprin: Kinetics of heterogeneous esterification

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