A CaO/zeolite-based catalyst obtained from waste chicken eggshell and coal fly ash for biodiesel production

•Synthesis of vishnevite-type zeolite-like material (ZM) from waste fly ash (FA).•Use of waste chicken eggshell as an active component in the CaO/FA-ZM catalyst.•Methanol/oil molar ratio of 6:1 was found optimal in methanolysis over CaO/FA-ZM.•FAME content of 97.5% was achieved for 1 h under moderat...

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Bibliographic Details
Published in:Fuel (Guildford) 2020-05, Vol.267, p.117171, Article 117171
Main Authors: Pavlović, Stefan M., Marinković, Dalibor M., Kostić, Milan D., Janković-Častvan, Ivona M., Mojović, Ljiljana V., Stanković, Miroslav V., Veljković, Vlada B.
Format: Article
Language:English
Subjects:
Autoclaving
Biodiesel
Biodiesel fuels
Biofuels
Calcium
Calcium oxide
Calcium silicates
Catalysts
Chemical synthesis
Chickens
Crystallography
Dehydration
Dicalcium silicate
Egg shells
Eggshell
Fly ash
Kinetic modeling
Lignite
Mass transfer
Mercury
Methanolysis
Poultry
Reaction mechanisms
Sodalite
Triglycerides
Waste materials
Zeolites
Zeolitic material
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Summary:•Synthesis of vishnevite-type zeolite-like material (ZM) from waste fly ash (FA).•Use of waste chicken eggshell as an active component in the CaO/FA-ZM catalyst.•Methanol/oil molar ratio of 6:1 was found optimal in methanolysis over CaO/FA-ZM.•FAME content of 97.5% was achieved for 1 h under moderate reaction conditions.•Kinetics based on changing mechanism and TAG mass transfer limitation was proven. The present paper is focused on the development of a new environment-friendly methanolysis catalyst completely based on waste materials: lignite coal fly ash and chicken eggshells. A novel catalyst based on CaO supported on a fly ash-based zeolitic material (CaO/FA-ZM) was obtained from a cancrinite-sodalite group zeolite-like material (vishnevite type) and active CaO by alkali activation in a new miniature autoclave reactor system and hydration-dehydration. Agitation by rotation of the entire reaction mixture led to a more homogeneous zeolitic product and saved both time and energy. The obtained catalyst structure corresponds to gismondine and the crystallographic modification of calcium silicate (α’-dicalcium silicate) with deposited CaO. The characteristics of the synthesized catalyst were determined using ED-XRF, XRD, FT-IR, SEM, Hg-porosimetry, N2-physisorption, LDPSA, and Hammett indicators. The CaO/FA-ZM catalyst exhibited a high activity (97.8% of FAME for only 30 min) and stability (a negligible drop in activity in five consecutive cycles) in the methanolysis reaction under the optimal reaction conditions (temperature of 60 °C, methanol/oil molar ratio of 6:1, and catalyst concentration of 6 wt%). A kinetic study was performed using two different mechanisms: the irreversible pseudo-first-order reaction mechanism in two regimes (heterogeneous and homogeneous) and the changing mechanism combined with the triacylglycerol mass transfer limitation. Both models showed a satisfactory agreement between the experimental and predicted values of conversion degree (R2 > 0.93), confirming their validity for the CaO-based heterogeneously catalyzed methanolysis. The values of the activation energy calculated for both mechanisms were 67.17 and 58.03 kJ mol−1, respectively.
ISSN:0016-2361
1873-7153
DOI:10.1016/j.fuel.2020.117171