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Valorization of eggshell waste to metal-doped CaO catalysts for producing dimethyl carbonate by transesterification of propylene carbonate with methanol
(2026-05-01)
Seeharaj, Panpailin
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Werupho, Sakila
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Puyamsai, Araya
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Choengchan, Nathawut
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Kim-Lohsoontorn, Pattaraporn
To align with a circular economy, this study aimed to extend the lifecycle of eggshell waste by valorizing it into a catalyst for producing the green chemical dimethyl carbonate (DMC) through the transesterification of propylene carbonate (PC) with methanol. CaO derived from eggshells was modified by doping with 10 mol% of aliovalent metal cations, including Na+, Mg2+, and Ce3+, via a calcination-hydration-dehydration process. The catalyst activity was tested under atmospheric air at 40–70 °C for 1–3 h. Metal-doped CaO possessed better activity than pure CaO, and the performance was ranked in order as CaO < Na–CaO < Ce–CaO < Mg–CaO. At the optimized reaction conditions of 50 °C for 2 h, the Mg–CaO catalyst exhibited the best performance, with 77% PC conversion, 62% DMC selectivity, and 37% DMC yield. This improvement correlated with the high surface-active area and optimum basicity induced by incorporating Mg2+ into the CaO structure and forming MgO–CaO mixed oxide phases. This study demonstrated a greener process for producing DMC under mild conditions using metal-doped CaO catalysts derived from eggshell waste.
1
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Valorisation of glycerol by-product of biodiesel production from crude palm oil (CPO) by catalytic conversion
(2024-04-11)
Nada, Shofiyah
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Juwono, Hendro
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Ritvirulh, Chonlada
Valorisation of glycerol through catalytic conversion conducted using KOH base catalysts with a mass ratio of KOH/glycerol of 0.08 (w/w) was carried out at temperature variations of 230 °C and 300 °C with feedstock variations of pure glycerol (98%) and crude glycerol with a total reaction time of 2 hours. Crude glycerol was obtained from the by-product of biodiesel transesterification from crude palm oil (CPO) using a KOH catalyst of 1% by weight of crude palm oil with variations in CPO:methanol such as 1:3, 1:6, and 2:1, which were performed at 60 °C for 4 hours at stirring speeds of 400 rpm. The largest percentage of crude glycerol conversion was obtained from the variation CPO: methanol (2:1) of 30.67%. The GC-MS characterization of glycerol catalytic conversion products revealed that the highest yield percentage is on the variation of pure glycerol feedstock at 230 °C, with the long-chain hydrocarbon fraction in the form of stearic acid compounds having the highest abundance percentage (abundance percentage of 26.54%). Catalyticconversion of pure glycerol feedstock variations at a reaction temperature of 300 °C resulted in formic acid (abundance percentage of 24.68%) with the greatest abundance and oxalic acid (abundance percentage of 2.28%). Meanwhile, the feedstock variation of crude glycerol produced 2-propenoic acid (abundance percentage of 5.04%) and acetone (abundance percentage of 2.84%), as well as hexadecanoic acid with the largest abundance percentage (32.04%). These findings demonstrated that catalytic glycerol conversion with KOH catalysts produced compounds with a wide range of industrial applications.
1
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Ultrasonic enhancement of lipase-catalyzed transesterification for biodiesel production from used cooking oil
(2023-06-01)
Patchimpet, Jaran
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Zhang, Yi
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Simpson, Benjamin K.
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Rui, Xin
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Sangkharak, Kanokphorn
This work investigated the ultrasonic irradiation-enhanced transesterification using lipase from the viscera of Nile tilapia (Oreochromis niloticus) to produce biodiesel from used cooking oil (UCO) and methanol. The effects of processing conditions such as irradiation time, ultrasonic frequency, and temperature on biodiesel yield were investigated. Results showed that the use of ultrasound decreased the reaction time from 28 to 3 h with ultrasonic frequency of 16 kHz, methanol to oil molar ratio of 4:1, lipase concentration of 30 kUnit, and reaction temperature of 40 °C. The efficacy of ultrasound was compared with conventional mechanical stirring operated at optimum conditions, and the ultrasonic irradiation coupled with stirring enhanced the transesterification with the highest yield of 97.59%. The fuel properties of the produced biodiesel in this study desirably met the recommended biodiesel standards as prescribed by EN 14214 and ASTM D 6751, suggesting the biodiesel obtained from ultrasound-assisted lipase-catalyzed transesterification of UCO with methanol is a promising alternative for conventional biodiesels and diesels. Graphical abstract: [Figure not available: see fulltext.].
1
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Supercritical reaction between methanol and glycerol: The effects of reaction products on biodiesel properties
(2021-12-01)
Sakdasri, Winatta
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Ngamprasertsith, Somkiat
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Saengsuk, Pongrawee
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Sawangkeaw, Ruengwit
This work investigated the supercritical reaction between glycerol and supercritical methanol (SCM) in non-catalytic biodiesel production process. Glycerol is a by-product of biodiesel production that could react with SCM, producing glycerol ethers (GEs). Simultaneous conversion of triglycerides and glycerol in SCM is promising to reduce the glycerol surplus. These GEs are completely miscible with biodiesel and work as fuel enhancer. In a batch reactor, the glycerol reaction with SCM was investigated between 325 °C and 400 °C. The methanol-to-glycerol molar ratios and reaction time were varied from 3:1 to 9:1 and 8 min to 12 min, respectively. It was observed that the reactions of glycerol and SCM were etherification, dehydration, and thermal decomposition of glycerol. At molar ratios of 3:1 and 6:1, the temperature and reaction time significantly enhanced the glycerol conversion, especially by the thermal decomposition reaction. The increasing methanol-to-glycerol molar ratios reduced the overall glycerol conversion. The maximum glycerol conversion of 46.40% was observed at reaction temperature of 400 °C, methanol-to-glycerol molar ratio of 3:1, and reaction time of 12 min. Besides, the effects of GEs-to-neat biodiesel (B100) volumetric ratios on the fuel properties were investigated. The blending of GEs positively improved the viscosity and cloud point, whereas it had no impact on the heating value and flash point.
2
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Water influence on the kinetics of transesterification using CaO catalyst to produce biodiesel
(2021-07-15)
Anantapinitwatna, Ajala
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Ngaosuwan, Kanokwan
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Kiatkittipong, Worapon
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Wongsawaeng, Doonyapong
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Anantpinijwatna, Amata
This research investigated the water influence on biodiesel production via transesterification, and especially on their kinetic parameters. The initial rate of transesterification was increased with increasing amount of water (0–5 wt%). On the contrary, the initial rate was significantly reduced for the water concentration of 8–15 wt%. Moreover, when the biodiesel yield reached the maximum value of 30–40%, saponification as a side reaction became more significant with the presence of the emulsion phase, resulting in a remarkable decrease in biodiesel yield. The simple kinetic model including the rate constant and apparent activation energy revealed that transesterification containing 5 wt% water gave the higher rate constant compared to the case with the absence of water. However, the simple model could not describe the case with high water content. The water effect should be accounted for in the reaction rate in the adsorption term. The modified Langmuir-Hinshelwood kinetic model including the effects of water contamination was originally proposed. Our finding suggested that despite the small amount of water content in transesterification using CaO catalyst giving rise in the initial rate, the water contamination in feedstocks for biodiesel production should be avoided because of the notable presence of saponification.
1
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Conversion of palm oil into biodiesel production with heterogeneous catalyst derived from spent coffee grounds ash: Process optimization through response surface methodology
(2021-01-01)
Jitjamnong, Jakkrapong
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Numwong, Natthida
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Chuaykarn, Narinphop
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Direksilp, Chatrawee
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Luengnaruemitchai, Apanee
In the present study, the calcination of spent coffee grounds (SCG) supporting potassium hydroxide and potassium carbonate (K<inf>2</inf>CO<inf>3</inf>) was used as a novel solid heterogeneous catalyst to convert palm oil to fatty acid methyl ester. The response surface method based on Box Behnken experimental design was used to optimize the biodiesel yield. The prepared catalyst was characterized by scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analyses. EDS analysis of the synthesis catalyst exhibited the presence of active potassium species for high catalytic activity. The 30K/SCG–600 catalysts exhibited the highest catalytic activity and were rich in K that formed a basic heterogeneous catalyst and the highest total basicity. The effects of catalyst loading (4.5–5.5 wt.%), methanol to oil molar ratio (6:1–12:1), and reaction time (60–120 min) on the transesterification were investigated. The results showed that the predicted optimum response for biodiesel yield from RSM was 97.01%, which could be obtained using methanol: oil molar ratio of 6.68:1, catalyst loading of 4.94 wt.%, and reaction time at 82.42 min. The actual biodiesel conversion of 97.08% was achieved under the predicted optimal conditions. The results of various statistics employed with high R2 (95.07%) and R2adj (88.73%) values indicated that the predicted and actual biodiesel yield was accurate and reliable.
1
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A review on insights for green production of unconventional protein and energy sources derived from the larval biomass of black soldier fly
(2020-05-01)
Hasnol, Sabrina
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Kiatkittipong, Kunlanan
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Kiatkittipong, Worapon
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Wong, Chung Yiin
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Khe, Cheng Seong
The purpose of this review is to reveal the lipid and protein contents in black soldier fly larvae (BSFL) for the sustainable production of protein and energy sources. It has been observed from studies in the literature that the larval lipid and protein contents vary with the rearing conditions as well as the downstream processing employed. The homogenous, heterogenous and microbial-treated substrates via fermentation are used to rear BSFL and are compared in this review for the simultaneous production of larval protein and biodiesel. Moreover, the best moisture content and the aeration rate of larval feeding substrates are also reported in this review to enhance the growth of BSFL. As the downstream process after harvesting starts with larval inactivation, various related methods have also been reviewed in relation to its impact on the quality/quantity of larval protein and lipids. Subsequently, the other downstream processes, namely, extraction and transesterification to biodiesel, are finally epitomized from the literature to provide a comprehensive review for the production of unconventional protein and lipid sources from BSFL feedstock. Incontrovertibly, the review accentuates the great potential use of BSFL biomass as a green source of protein and lipids for energy production in the form of biodiesel. The traditional protein and energy sources, preponderantly fishmeal, are unsustainable naturally, pressingly calling for immediate substitutions to cater for the rising demands. Accordingly, this review stresses the benefits of using BSFL biomass in detailing its production from upstream all the way to downstream processes which are green and economical at the same time.

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