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Optimization of hydrothermal carbonization of Rhizoclonium riparium macroalgae using response surface methodology for high-performance solid biofuel production
(2026-01-01)
Chanpee, Sirayu
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Jadsadajerm, Supachai
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Manatura, Kanit
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Wongrerkdee, Sutthipoj
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Eiad-ua, Apiluck
Hydrothermal carbonization (HTC) was adopted as a promising approach for improving fuel quality for several high-moist biomass. In this study, the Rhizoclonium riparium macroalgae (RMA), an abundant marine alga in an aquaculture pond, was successfully converted into hydrochars as a sustainable solid biofuel. The Box Behnken design (BBD) was applied for the HTC experiment to investigate the individual and interactive effects of operating parameters, including HTC temperature, reaction time, and water ratio, on hydrochar physicochemical characteristics and fuel properties. The response surface optimization (RSM) revealed maximum mass yield (MY) of 79.1%, higher heating value (HHV) of 23.6 MJ/kg, and energy yield (EY) of 94.4%. The RSM-BBD of process parameters and their HTC effects showed that the decreasing MY and EY were significantly due to the HTC temperature and residence time. From ANOVA analysis, temperature, time, and water ratio were the most significant parameters responding to MY, HHV, and EY. The optimal conditions for hydrothermal carbonization (HTC) of RMA as a solid biofuel were determined to be a temperature of 200 °C, a duration of 2 h, and a water-to-biomass ratio of 1:1, producing the highest energy yield (EY) of 95.3%. Utilizing RSM-BBD to investigate HTC parameters for hydrochar production is a suitable effort for technical scalability.
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Oil palm leaf-derived nanoporous carbon via hydrothermal carbonization combined with NaOH microwave activation for tetracycline adsorption
(2025-11-01)
Chanpee, Sirayu
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Apinyakul, Naruemon
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Kaewtrakulchai, Napat
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Khemasiri, Narathon
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Eiad-ua, Apiluck
Generally, the increase in pharmaceutical industrial activities has led to a corresponding rise in water resource contamination. Efforts have been dedicated to addressing the urgent challenge of waste biomass disposal by developing recycling methods capable of producing bio-adsorbents. Adsorption is a promising approach for removing tetracycline contaminants, owing to its simplicity, stability, and cost-effectiveness. In this study, a low-cost activated biochar was successfully developed using oil palm leaf (OPL) via hydrothermal carbonization (HTC) combined microwave-assisted pyrolysis system (MAPS) using sodium hydroxide (NaOH). The HTC and MAPS processes enhanced high mass yield, porosity, energy efficiency, and reduced reaction time. NaOH treatment improved the porosity of the activated biochar derived from OPL, resulting primarily in a mesoporous structure. However, NaOH treatment via the MAPS process increased surface area and porosity. Among the samples tested, OPLC-NaOH-1:1 exhibited the largest surface area and highest porosity, making it the chosen candidate for further TC adsorption tests. The adsorption experiments revealed that the Langmuir isotherm model and the pseudo-second-order kinetic model accurately matched the experimental data, suggesting a mono-layered adsorption mechanism due to micropores and chemisorption interactions. Additionally, thermodynamic analysis indicated an endothermic and spontaneous reaction during the adsorption process. The adsorption of nanoporous carbon for TC was primarily regulated by pore filling, hydrogen bonding, electrostatic effects, and π-π interactions also playing a significant role. Overall, this study highlights the potential of utilizing OPL waste as a sustainable material for producing nanoporous carbon and underscores the effectiveness of nanoporous carbon for adsorbing antibiotics.
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Solid shrimp waste derived nanoporous carbon as an alternative bio-sorbent for oxytetracycline removal from aquaculture wastewater
(2024-06-15)
Kaewtrakulchai, Napat
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Samattakarn, Nippit
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Chanpee, Sirayu
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Assawasaengrat, Pornsawan
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Manatura, Kanit
Recently, it has been critical to effectively remove oxytetracycline (OTC) from aquaculture wastewater before releasing into the environment. The adsorption process is recognized as an efficient pathway for removing OTC since it is a simple, stable, and cost-effective method. This study aims to develop nanoporous carbon entirely from shrimp waste (SW) via hydrothermal carbonization assisted with KOH activation. Existing KOH significantly increases the porosity of SW nanoporous carbon. The optimal SW porous carbon was obtained using 5 wt%KOH for activation, which had the largest surface area of 679.51 m2/g with the total pore volume of 0.458 cm3/g. Moreover, the SW porous carbon with the highest porosity was selected for the OTC adsorption. The Langmuir isotherm model and the pseudo-second-order kinetic model match the experimental data, implying that the adsorption mechanism is mono-layered adsorption due to micropores by chemisorption interaction. The adsorption capacity significantly improved by increasing the dosage of SW nanoporous carbon. The SW nanoporous carbon adsorption for OTC is primarily regulated by pore filling affected by hydrogen bonding, and π-π* interaction also plays a significant role. The SW nanoporous carbon showed an efficient OTC adsorption after 5 regeneration cycles. This work demonstrates biomass waste recycling and emphasizes the potential of aquatic food processing waste-derived nanoporous carbon for antibiotic adsorption.
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Synthesis of nanoporous carbon from brewer waste by hydrothermal carbonization assisted chemical activation for carbamazepine adsorption
(2024-06-01)
Apinyakul, Naruemon
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Chanpee, Sirayu
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Kaewtrakulchai, Napat
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Khemasiri, Narathon
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Eiad-ua, Apiluck
Nanoporous carbon (NPC) has gained significant attention in wastewater treatment due to its effectiveness. The adsorption process, known for its simplicity, stability, and cost-effectiveness, is widely recognized as an efficient method for removing carbamazepine (CBZ) residues accumulate in the environment. However, the application of NPC is often hindered by challenges in the regeneration process after use, as well as issues related to large surface area, pore size, and functional groups. Fortunately, the samples in this study not only maintained their adsorption efficiency but also demonstrated the ability to be regenerated multiple times. Herein brewery waste was subjected to hydrothermal treatment at 200 °C for 1 h and followed by KOH and NaCl activation with different KOH:NaCl (w/w) ratios of 5:0, 4:1, 3:2, 1:1, 2:3, 1:4, and 0:5 to optimize the properties of malt husk derived nanoporous carbon (NPC). The optimal condition KOH:NaCl ratio of 1:1 had a maximum specific surface area of 906 m2/g with a total pore volume of 0.252 cm3/g. According to the adsorption test, the CBZ adsorption isotherm was well-fitted to the Langmuir model (R2 = 0.976) kinetic data were consistent with the pseudo-second-order model (R2 = 0.995). This suggests that the adsorption mechanism involves monolayer adsorption and chemisorption interaction. The Gibbs free energy and enthalpy of CBZ adsorption by NPC were found to be spontaneous and endothermic. The regeneration test revealed a 95.35% decrease in the adsorption capacity of NPC after 5 repeated cycles. Consequently, the study suggests a potential application of nanoporous carbon from MH as an alternative adsorbent for removing carbamazepine in wastewater.
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Bimetallic PdNi catalyst on cattail Leaves-Derived nanoporous carbon support for synthesis of partially hydrogenated fatty acid methyl ester (H-FAME)
(2024-06-01)
Longprang, Tripob
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Kaewtrakulchai, Napat
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Kiatkittipong, Worapon
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Srifa, Atthapon
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Chollacoop, Nuwong
Cattail leaves (CL) have been used as a carbon source to synthesize nanoporous carbon (NPC) support with high surface area (S<inf>BET</inf> = 2002.12 m2g−1) via hydrothermal carbonization and potassium hydroxide (KOH) activation. The studied catalysts, including monometallic Pd/NPC and Ni/NPC, and bimetallic PdNi/NPC, were synthesized and characterized by using several techniques (e.g., scanning electron microscopy, transmission electron microscopy, nitrogen sorption, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction). Their catalytic activity toward partial hydrogenation of palm biodiesel to H-FAME was tested, and the liquid product composition, cloud point, and oxidation stability were determined. The studied catalysts have a high porosity with the S<inf>BET</inf> of approximately 2037.34–2187.96 m2g−1 led to excellent metal dispersion. Although Ni did not show high catalytic activity compared to Pd, Ni incorporated with Pd as PdNi/NPC catalyst significantly increased the cis-C18:1 selectivity and prevented the catalytic deactivation during the partial hydrogenation. The oxidation stability of palm biodiesel feedstock was increased from 13.69 to 17.12 h while the cloud points adversely increased by only 3 degrees from 12 to 15 °C (still lower than 16 °C of the Thai industrial recommendation) with bimetallic PdNi/NPC catalyst. The main benefit of bimetallic PdNi/NPC over monometallic Pd/NPC and Ni/NPC is shown through not only higher C18:2 conversion but also much higher cis-to-trans ratio of C18:1 resulting in higher oxidation stability with acceptable compromise on the cloud point increasing. Consequently, the produced palm H-FAME can be used at a high blend ratio.
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Enhanced Removal of Phosphorus from Aqueous Solutions by Cation-Modified Hydrochar
(2023-10-01)
Wutthipattarathorn, Kamyaporn
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Thawornchaisit, Usarat
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Janyapoon, Suwannee
In this study, cassava stem-derived hydrochar was modified with sodium hydroxide (NaOH) treatment, followed by loading of minerals, was used to prepare cation-modified hydrochars with enhanced phosphate removal ability. Cassava stems were converted to hydrochar by hydrothermal carbonization at 240 °C for 60 min, then it was soaked in 2 M NaOH for 3 h. The NaOH-treated hydrochars were then loaded with iron (Fe), magnesium (Mg) and calcium (Ca). The cassava stems and the derived hydrochars were analyzed for carbon, hydrogen, nitrogen and oxygen content, surface morphology and elemental compositions. Methylene Blue Numbers (MBN) measured surface area and porosity, and pH at the point of zero charge (pHpzc) was determined. Modification with Fe, Mg and Ca improved phosphate removal efficiency of the resulting hydrochars. Treatment of synthetic wastewater containing 50 mg P/L at pH 7 with the dosage of 2 g/L of the cation-modified hydrochars for 360 min showed that phosphate removal efficiency of these modified hydrochars were-Fe-modified 81 %, Mg-modified 66 % and Ca-modified 56 %. When the adsorbent dosage increased to 20 g/L, more than 98 % of phosphate was removed by the hydrochars modified with Fe, Ca and Mg. In the same conditions, phosphate removal efficiency was for the NaOH-treated hydrochars-89 %, hydrochar derived from cassava steam-69 % and the starting material-59 %. The phosphate removal ability of these cation-modified hydrochars increased even when initial phosphorus concentration was increased to 100 mg P/L. This work demonstrated that an abundant agricultural residue, cassava stems, can be converted into effective phosphate adsorbents.
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High performance nanoporous carbon from mulberry leaves (Morus alba L.) residues via microwave treatment assisted hydrothermal-carbonization for methyl orange adsorption: Kinetic, equilibrium and thermodynamic studies
(2022-03-01)
Siraorarnroj, Siwat
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Kaewtrakulchai, Napat
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Fuji, Masayoshi
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Eiad-ua, Apiluck
High performance nanoporous carbons were directly prepared from mulberry leaves (Morus alba L.) residues by the hydrothermal-carbonization with chemical reagent combined the microwave-assisted treatment. The as-purified ML porous carbon (MPC) was successfully applied for the adsorption of methyl orange, which is one of crucial waste-water pollutants left from an industrial sector. The MPC sample obtained from the hydrothermal process (200 °C, 12 h) using an activation of 15 wt% NaOH (700 °C, 2 h), and combined with microwave treatment at 700 W for 6 min, specifically exhibited micropores and mesopores in the MPC morphological structure. Accordingly, the highest S<inf>BET</inf> was approximately 791.79 m2/g with the total pore volume of 0.495 cm3/g. Moreover, the adsorption performance test of MPC was conducted by the shaking unit using 100 ppm methyl orange concentration. The MPC showed the highest methyl orange-adsorption uptake of 99% at 30 °C under an ambient pressure (1 atm). The development of mulberry leaves (Morus alba L.) residues into porous carbon exhibited a great attention for dyes adsorption with a rapid adsorption kinetic, and excellent adsorption capacity, which are a promising-characteristics for practical waste-water adsorption experiments.
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Sugarcane bagasse-derived hydrochar: Modification with cations to enhance phosphate removal
(2021-09-01)
Thawornchaisit, Usarat
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Onlamai, Tanrawee
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Phurkphong, Nontakorn
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Sukharom, Rawiwan
Cation modified hydrochars were synthesized by hydrothermal carbonization (HTC) of sugarcane bagasse, followed by impregnation of three different cations (Ca, Mg, and Fe) or co-precipitation of Fe3+ and Fe2+. HTC enhanced the hydrochar surface area and increased the enrichment of oxygen functional groups on the hydrochar surface confirmed by FTIR. The oxygen functional groups further improve the adsorption capacity for cations during hydrochar chemical modification. Physical appearance, FTIR and XRF confirmed that Ca2+, Mg2+ and Fe2+ or Fe3+ were well retained in the bagasse-derived hydrochar. The pH<inf>pzc</inf> values of all chemically modified hydrochars were greater than the unmodified hydrochar or bagasse alone. Modification with different cations improved phosphate uptake capacity. The Fe-modified hydrochar with about 45-50% Fe content showed greater phosphate removal efficiency than Ca-and Mg-modified hydrochars. In addition, hydrochars decorated by impregnation of Fe3+ demonstrated better phosphate removal than ones produced by co-precipitation of Fe3+ and Fe2+. Thus, chemically modified hydrochars could be used as an environmentally alternative adsorbent for phosphate removal from aqueous solutions.
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Influence of Acid Additive on Nanoporous Carbon Materials via HTC for Catalyst Support
(2020-01-01)
Longprang, Tripob
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Jaruwat, Dolrudee
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Udomsap, Parncheewa
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Chollacoop, Nuwong
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Eiad-Ua, Apiluck
Nanoporous carbon materials were successfully synthesized via hydrothermal carbonization with acid additives. In this study the effect of hydrothermal temperature (160-200 °C), hydrothermal time (4-24 h) and influence of acid additive (HCl, HNO<inf>3</inf>, H<inf>2</inf>SO<inf>4</inf> and H<inf>3</inf>PO<inf>4</inf>) have been chosen in order to improve the surface structure. The samples have been characterized by scanning electron microscopy, nitrogen sorption, Fourier transform infrared spectroscopy and X-ray diffraction. The experimental results revealed that hydrothermal carbonization process and acid addition have effect on the properties of catalyst support. The results indicated that hydrothermal process at 200°C for 12 h and activation with H<inf>3</inf>PO<inf>4</inf> at 900 °C for 2 h, exhibited the highest surface area, porosity and pore volume leading to increased distribution of metal on the carbon support.
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Fundamental study of carbon materials from empty fruit bunch via hydrothermal carbonization with H3PO4 and naoh activation
(2020-01-01)
Guntagerng, Kanogpan
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Panomsuwan, Gasidit
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Fuji, Masayoshi
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Eiad-ua, Apiluck
Lignocellulosic biomass has great potential as an energy source or feedstock for further conversion. Empty fruit bunches (EFBs) were agricultural waste materials from palm oil production. In this research, we aim to study the morphology of hydrochars derived from EFBs via hydrothermal treatments with phosphoric acid (H<inf>3</inf>PO<inf>4</inf>) and sodium hydroxide (NaOH) activation at different concentrations (i.e., 0.5, 0.7, and 1 M) at 200°C for 12 h, followed by carbonization at 700°C under nitrogen atmosphere for 2 h. The samples were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and specific surface analysis. After carbonization, the hydrochar activated by 1.0 M H<inf>3</inf>PO<inf>4</inf> possessed the highest surface area of 590 m2/g with the dominance of micropores. Hydrothermal carbonization with acid-base activation showed an effective method in preparing high porous activated carbon from EFB.

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