The volumetric adsorption kinetics of carbon dioxide (CO2) onto the synthesized palm kernel shell activated carbon via single-stage CO2 activation and commercial Norit® activated carbon were carried out at an initial pressure of approximately 1 bar at three different temperatures of 25, 50, and 100 °C. The experimental kinetics data were modelled by using the Lagergren's pseudo-first-order model and pseudo-second-order model. Comparing these two, the non-linear pseudo-second-order kinetics model presented a better fit towards CO2 adsorption for both adsorbents, owing to its closer coefficient of determination (R2) to unity, irrespective of the adsorption temperature. In addition, kinetics analysis showed that the corresponding kinetics coefficient (rate of adsorption) of both activated carbons increased with respect to adsorption temperature, and thereby, it indicated higher mobility of CO2 adsorbates at an elevated temperature. Nevertheless, CO2 adsorption capacity of both activated carbons reduced at elevated temperatures, which signified exothermic and physical adsorption (physisorption) behaviour. Besides, process exothermicity of both carbonaceous adsorbents can be corroborated through activation energy (Ea) value, which was deduced from the Arrhenius plot. Ea values that were in range of 32-38 kJ/mol validated exothermic adsorption at low pressure and temperature range of 25-100 °C. To gain an insight into the CO2 adsorption process, experimental data were fitted to intra-particle diffusion model and Boyd's diffusion model, and findings revealed an involvement of both film diffusion and intra-particle diffusion during CO2 adsorption process onto the synthesized activated carbon and commercial activated carbon.
Accelerating greenhouse gas emission particularly carbon dioxide (CO2) in the atmosphere has become a major concern. Adsorption process has been proposed as a promising technology for CO2 adsorption from flue gas, and the carbonaceous adsorbent is a potential candidate for CO2 adsorption at atmospheric pressure and ambient temperature. Biochar derived from palm kernel shell waste was applied as a potential precursor for activated carbon production. This research study employed the response surface methodology coupled with Box-Behnken design to optimize the parameters involved in producing exceptional activated carbon with high yield (Y1) and CO2 adsorptive characteristics (Y2). Specifically, parameters studied include the activation temperature (750-950 °C), holding time (60-120 min), and CO2 flow rate (150-450 mL/min). The activated carbon at the optimum conditions was characterized using various analytical instruments, including elemental analyzer, nitrogen (N2) physisorption analyzer, and field emission scanning electron microscopy. Overall, utilization of biochar as the activated carbon precursor is practical compared with the traditional non-renewable materials, due to its cost efficiencies and it being more environment-friendly ensuring process sustainability. Besides, this research study that incorporates physical activation with CO2 as the activating agent is attractive, because it directly promotes CO2 utilization and capture, in addition to the absence of any chemicals that may result in the secondary pollution problems.
A novel titanium dioxide/activated carbon (TiO2/AC) composite where AC derived from oil palm empty fruit bunch (EFB) was synthesised by using sol-gel method. All the samples were characterised by using X-ray diffraction (XRD), scanning electron microscopy-energy dispersive X-ray (SEM-EDX), Fourier transformed infrared (FTIR), thermogravimetric analysis (TGA) and surface analyser. SEM analysis showed that TiO2 particles were successfully embedded and well distributed on the AC surface. The elemental composition analysis found that the TiO2/AC composite contained titanium (Ti), oxygen (O) and carbon (C) atoms. Meanwhile, the appearance of new band at about 960 cm-1 which assigned to the Ti-O stretching was observed in the FTIR spectra when the AC was incorporated into TiO2. TGA analysis showed that the weight loss of 32 wt.% from 150 to 550 °C was due to the decomposition of amorphous carbon layers and loss of hydroxyl groups on TiO2. It was found that the TiO2/AC composite had better performance in the sonocatalytic degradation of malachite green as compared to the individual AC and TiO2 because the TiO2/AC composite had dual functionality and huge number of active sites which could promote the mass transfer of dye molecules towards catalyst surface. By using 1.5 g/L of TiO2/AC composite which calcined at 700 °C on 100 mL of 200 mg/L of malachite green at solution pH of 7, a degradation efficiency of 87.11% had been achieved after 30 min of ultrasonic irradiation. A lower chemical oxygen demand (COD) removal (81.75%) was observed because the structured dye molecules underwent mineralisation process during the sonocatalytic degradation to generate intermediate compounds. The TiO2/AC composite was able to be recycled and still achieved a high degradation efficiency of 76.78% after second catalytic cycle as compared to the fresh TiO2/AC composite with degradation efficiency of 87.11%. In conclusion, the TiO2/AC composite had high reusability and promising for practical applications in textile industry.
Nickel-iron doped granular activated carbon (GAC-N) was used to enhance immobilization in biohydrogen production. The effect of the sludge ratio to GAC-N, ranged 1:0.5-4, was studied. The optimum hydrogen yield (HY) of 1.64 ± 0.04 mol H2/mol sugar consumed and hydrogen production rate (HPR) of 45.67 ± 1.00 ml H2/L.h was achieved at a ratio of 1:1. Immobilization study was performed at 2 d HRT with a stable HY of 2.94 ± 0.16 mol H2/mol sugar consumed (HPR of 83.10 ± 4.61 ml H2/L.h), shorten biohydrogen production from 66 d to 26 d, incrementing HY by 57.30 %. The Monod model resulted in the optimum initial sugar, maximum specific growth rate, specific growth rate, and cell growth saturation coefficient at 20 g/L, 2.05 h-1, 1.98 h-1 and 6.96 g/L, respectively. The dominant bacteria identified was Thermoanaerobacterium spp. The GAC-N showed potential as a medium for immobilization to improve biohydrogen production.
This study investigates a prospective and straightforward method for producing graphene material derived from biomass, examining the influence of plant cell composition and functions. The experimental outcomes highlight ultrasound's crucial role in synthesizing graphene material sourced from biomass. Ultrasound, a pivotal element in the experiment, significantly affects graphene production from biomass by working synergistically with the liquid components in the solvent system. Notably, the ethanol content reduces the solution's surface tension, facilitating the effective dispersion of biochar and graphene oxide sheets throughout the process. Simultaneously, the water content maintains the solution's polarity, enhancing the cavitation effect induced by ultrasound. Biomass-derived graphene is exfoliated utilizing an ultrasonic bath system (134.4 W, 40 kHz, 0.5 W/cm2) from biochar. The as-synthesized graphene oxide exhibits a structure comprising a few layers while remaining intact, featuring abundant functional groups. Interestingly, the resulting product displays nanopores with an approximate diameter of 100 nm. These nanopores are attributed to preserving specific cell structures, particularly those with specialized cell wall structures or secondary metabolite deposits from biomass resources. The study's findings shed light on the impact of cellular structure on synthesizing graphene material sourced from biomass, emphasizing the potential application of ultrasound as a promising approach in graphene production.
Polycyclic aromatic hydrocarbons (PAHs) are critical environmental concerns due to their intrinsic toxic aromatic nature and concomitant circumstances that potentially harm the ecological and human health. In this study, converting mahogany (Swietenia macrophylla King) pericarps to value-added biochar by pyrolysis for evaluating the potential formation/destruction of biochar-bound PAHs was studied for the first time. This study designed and optimized the thermal processing conditions at 300-900 °C in the CO2 or N2 atmosphere, and heteroatoms (N, O, B, NB, and NS) were modified for mahogany pericarps biochar (MPBC) production. The MPBC500 exhibited significantly higher pyrolysis products of PAHs (2780 ± 38 ng g-1) than that of MPBC900 (78 ± 6 ng g-1) under N2 without introducing modified elements. Specifically, the inhibition capacity of MPBC500 for PAHs under CO2 was improved most efficiently by the active nitrogen species of the pyridinic N and pyrrolic N groups. The pyrolysis conditions and heteroatom modification of MPBC altered its physicochemical properties, that is, aromaticity and hydrophobicity, affecting the PAH concentration and composition in the pyrolysis products. This study reveals sustainable approaches to reduce the environmental footprint of biochar by focusing on increases in PAHs pollution in sustainable biochar produced from a low-carbon bioeconomy perspective.
Gua Sireh, located in western Sarawak (Malaysian Borneo), is known for its rock art. The cave houses hundreds of charcoal drawings depicting people, often with headdresses, knives and other accoutrements. Here, we present direct radiocarbon dates and pigment characterizations from charcoal drawings of two large (>75 cm), unique Gua Sireh human figures (anthropomorphs). To our knowledge, these are the first chronometric ages generated for Malaysian rock art, providing insights into the social contexts of art production, as well as the opportunities and challenges of dating rock art associated with the Malay/Austronesian diasporas in Southeast Asia more generally. Previous archaeological excavations revealed that people occupied Gua Sireh from around 20,000 years ago to as recently as AD 1900. The site is within Bidayuh territory, and these local Indigenous peoples recall the cave's use as a refuge during territorial violence in the early 1800s. The age of the drawings, dated between 280 and 120 cal BP (AD 1670 to 1830), corresponds with a period of increasing conflict when the Malay elites controlling the region exacted heavy tolls on the local hill tribes. We discuss rock art production at Gua Sireh in this context of frontier conflict and Bidayuh resistance.
This study presents an innovative method for synthesizing activated carbon with an exceptionally high surface area (3359 m2 g-1) using kenaf fiber-based biochar through chemical activation. The achieved specific surface area surpasses activated carbon derived from other reported fiber-based precursors. The resulting activated carbon was investigated as electrodes for supercapacitors, revealing a remarkable maximum capacitance of 312 F g-1 at a current density of 0.5 A g-1. An aqueous symmetric supercapacitor employing these high-surface-area electrodes exhibited an outstanding energy density of 18.9 Wh kg-1 at a power density of 250 W kg-1. Notably, the supercapacitor retained exceptional capacitance, maintaining 93% of its initial capacitance even after 5000 charge-discharge cycles.
This study developed six machine learning models to predict the biochar properties from the dry torrefaction of lignocellulosic biomass by using biomass characteristics and torrefaction conditions as input variables. After optimization, gradient boosting machines were the optimal model, with the highest coefficient of determination ranging from 0.89 to 0.94. Torrefaction conditions exhibited a higher relative contribution to the yield and higher heating value (HHV) of biochar than biomass characteristics. Temperature was the dominant contributor to the elemental and proximate composition and the yield and HHV of biochar. Feature importance and SHapley Additive exPlanations revealed the effect of each influential factor on the target variables and the interactions between these factors in torrefaction. Software that can accurately predict the element, yield, and HHV of biochar was developed. These findings provide a comprehensive understanding of the key factors and their interactions influencing the torrefaction process and biochar properties.
The influence of biomass cellulosic content on biochar nanopore structure and adsorption capacity in aqueous phase was scarcely reported. Commercial cellulose (100% cellulose), oil palm frond (39.5% cellulose), and palm kernel shell (20.5% cellulose) were pyrolyzed AT 630 °C, characterized and tested for the adsorption of iodine and organic contaminants. The external surface area and average pore size increased with cellulosic content, where commercial cellulose formed biochar with external surface area of 95.4 m2/g and average pore size of 4.1 nm. The biochar from commercial cellulose had the largest adsorption capacities: 371.40 mg/g for iodine, 86.7 mg/L for tannic acid, 17.89 mg/g for COD and 60.35 mg/g for colour, while biochar from palm kernel shell had the least adsorption capacities. The cellulosic content reflected the differences in biochar nanopore structure and adsorption capacities, signifying the suitability of highly cellulosic biomass for producing biochar to effectively treat wastewater.
Asteraceae presents one of the most globally prevalent, cultivated, and fundamental plant families. However, a large amount of agricultural wastes has been yearly released from Asteraceae crops, causing adverse impacts on the environment. The objective of this work is to have insights into their biomass potentials and technical possibility of conversion into biochars. Physicochemical properties are systematically articulated to orientate environmental application, soil amendment, and other utilizations. Utilizations of Asteraceae biochars in wastewater treatment can be categorized by heavy metal ions, organic dyes, antibiotics, persistent organic pollutants (POPs), and explosive compounds. Some efforts were made to analyze the production cost, as well as the challenges and prospects of Asteraceae-based biochars.
A series of batch laboratory studies were conducted to investigate the suitability of activated carbon SA2 for the removal of cadmium ions and zinc ions from their aqueous solutions. The single component equilibrium data were analyzed using the Langmuir and Freundlich isotherms. Overall, the Langmuir isotherm showed a better fitting for all adsorptions under investigation in terms of correlation coefficient and error analysis (SSE only 18.2 for Cd2+ and 47.95 for Zn2+). As the binary adsorption is competitive, extended Langmuir models could not predict the binary component isotherm well. The modified extended Langmuir models were used to fit the binary system equilibrium data. The binary isotherm data could be described reasonably well by the modified
extended Langmuir model, as indicated in the error analysis.
Biochar can be used for soil remediation in environmentally beneficial manner, especially when combined with nanomaterials. After a decade of research, still, no comprehensive review was conducted on the effectiveness of biochar-based nanocomposites in controlling heavy metal immobilization at soil interfaces. In this paper, the recent progress in immobilizing heavy metals using biochar-based nanocomposite materials were reviewed and compared their efficacy against that of biochar alone. In details, an overview of results on the immobilization of Pb, Cd, Cu, Zn, Cr, and As was presented by different nanocomposites made by various biochars derived from kenaf bar, green tea, residual bark, cornstalk, wheat straw, sawdust, palm fiber, and bagasse. Biochar nanocomposite was found to be most effective when combined with metallic nanoparticles (Fe3O4 and FeS) and carbonaceous nanomaterials (graphene oxide and chitosan). This study also devoted special consideration to different remediation mechanisms by which the nanomaterials affect the effectiveness of the immobilization process. The effects of nanocomposites on soil characteristics related to pollution migration, phytotoxicity, and soil microbial composition were assessed. A future perspective on nanocomposites' use in contaminated soils was presented.
This study examined an aquaponic approach of circulating water containing ammonia excretions from African catfish grown in an aquaculture tank for bacterial conversion into nitrates, which then acted as a nutrient substance to cultivate lettuce in hydroponic tank. We found that microwave pyrolysis biochar (450 g) having microporous (1.803 nm) and high BET surface area (419 m2/g) was suitable for use as biological carrier to grow nitrifying bacteria (63 g of biofilm mass) that treated the water quality through removing the ammonia (67%) and total suspended solids (68%), resulting in low concentration of remaining ammonia (0.42 mg/L) and total suspended solid (59.40 mg/L). It also increased the pH (6.8), converted the ammonia into nitrate (29.7 mg/L), and increased the nitrogen uptake by the lettuce (110 mg of nitrogen per plant), resulting in higher growth in lettuce (0.0562 %/day) while maintaining BOD5 level (3.94 mg/L) at acceptable level and 100% of catfish survival rate. Our results demonstrated that microwave pyrolysis biochar can be a promising solution for growing nitrifying bacteria in aquaponic system for simultaneous toxic ammonia remediation and generation of nitrate for growing vegetable in aquaculture industry.
The emission of waste anaesthetic gas is a growing contributor to global warming and remains a factor in atmospheric ozone depletion. Volatile anaesthetics in medical waste gases could be removed via adsorption using suitable activated carbon materials possessing an enhanced affinity to anaesthetic molecules. In this work, the effects of surface physical and chemical properties on sevoflurane adsorption were investigated by oxidative hydrothermal surface modification of a commercial activated carbon using only distilled water. The hydrothermal surface modification was carried out at different treatment temperatures (150-300 °C) for varying durations (10-30 min), and adsorption was conducted under fixed conditions (bed depth = 10 cm, inlet concentration = 528 mg/L, and flow rate = 3 L/min). The hydrothermal treatment generally increased the BET surface area of the activated carbons. At oxidation temperatures above 200 °C, the micropore volume of the samples diminished. The relative amount of surface oxygen was enriched as the treatment temperature increased. Treatment duration did not significantly affect the introduction of relative amount of surface oxygen, except at higher temperatures. There were no new types of functional groups introduced. However, disappearance and re-formation of oxygen functional groups containing C-O structures (as in hydroxyl and ether groups) occurred when treatment temperature was increased from 150 to 200 °C, and when treatments were conducted above 200 °C, respectively. The ester/acetal groups were enriched under the temperature range studied. The findings suggested that the re-formation of surface oxygen functionalities might lead to the development of functional groups that improve sevoflurane adsorption.
This study aims to produce biochar and sugars from a macroalga Eucheuma denticulatum using dilute sulfuric acid hydrolysis along with microwave-assisted heating. The reactions were operated at sulfuric acid concentrations of 0.1 and 0.2M, reaction temperatures of 150-170°C and a heating time of 10min. Compared to the raw macroalga, biochar qualities were improved with increased carbon content and lower ash and moisture contents. The calorific value of the biochar could be intensified up to 45%, and 39% of energy yield was recovered. Apart from producing biochar, the highest total reducing sugars were 51.47g/L (74.84% yield) along with a low by-product 5-HMF of 0.20g/L, when the biomass was treated under the optimum conditions at 160°C with 0.1M H2SO4. Thus, this study demonstrated that macroalgae could be potentially used as biomass feedstock under microwave-assisted acid hydrolysis for the production of biofuel and value-added products.
This work is scrutinizing the development of metallized biochar as a low-cost bio-sorbent for low temperature CO2 capture with high adsorption capacity. Accordingly, single-step pyrolysis process was carried out in order to synthesize biochar from rambutan peel (RP) at different temperatures. The biochar product was then subjected to wet impregnation with several magnesium salts including magnesium nitrate, magnesium sulphate, magnesium chloride and magnesium acetate which then subsequently heat-treated with N2. The impregnation of magnesium into the biochar structure improved the CO2 capture performance in the sequence of magnesium nitrate > magnesium sulphate > magnesium chloride > magnesium acetate. There is an enhancement in CO2 adsorption capacity of metallized biochar (76.80 mg g-1) compare with pristine biochar (68.74 mg g-1). It can be justified by the synergetic influences of physicochemical characteristics. Gas selectivity study verified the high affinity of biochar for CO2 capture compared with other gases such as air, methane, and nitrogen. This investigation also revealed a stable performance of the metallized biochar in 25 cycles of CO2 adsorption and desorption. Avrami kinetic model accurately predicted the dynamic CO2 adsorption performance for pristine and metallized biochar.
Removal of H2S (hydrogen sulfide) from biogas is anticipated for higher energy conversion of methane (CH4), while reducing the detrimental impacts of corroding the metal parts in the plant and its hazardous effect on humans and the environment. The introduction of microwave (MW) heating and nitrogen-modification could generate superior adsorbent features, contributing to high H2S removal. Up to date, there is no work reported on the influence of physicochemical characteristics of nitrogen-modified carbon synthesized via MW and conventional heating (TH) methods and their performance in H2S removal. Palm shell activated carbon (PSAC) was functionalized with nitrogen groups via urea impregnation, followed by the synthesis of MW and TH at 950 °C, 500 ml/min of N2 flow rate and 30 min of heating time. MW and TH heating effects on the modified PSAC adsorbent were analysed and compared towards hydrogen sulfide (H2S) removal. PSAC with nitrogen functionalization produced using MW heating (PSAC-MW) demonstrates superior performance, with an adsorption capacity of 356.94 mg/g. The adsorbent sample generated using MW heating exhibited notable properties, including a large surface area and a sponge-like structure, with new pores developed within the current pores. Instead of that, there was an observation of 'hot spot' appearance during the MW heating process, which is believed to be responsible for the development of physical and chemical characteristics of the adsorbent. Thus, it is believed that MW heating was assisted in the development of the adsorbent's properties and at the same time contributed to the high removal of H2S at low adsorption temperature. The utilization of biomass-based adsorbent (PSAC) for H2S removal can address the lignocellulosic waste disposal problem, while mitigating the H2S release from the biogas production plants thus has several environmental merits. This indirectly contributed to zero-waste generation, while overcoming the adverse effects of H2S.
The use of agricultural by-products such as Moringa oleifera plants is one effort to support the reduction of environmental pollution. Activated carbon produces from agricultural wastes is relatively less expensive and can replace traditional methods such as renewable as well as nonrenewable materials such as petroleum residue and coal. In this study, the removal of bisphenol A from aqueous media was studied using activated carbon produced from M. oleifera pods and peels. A batch adsorption study was carried out by varying the parameters of the adsorption process. A maximum removal percentage of 95.46% was achieved at optimum conditions of 2.5 g L-1 adsorbent dose, pH 7, 60 min contact time and 20 mg L-1 initial concentration of BPA. The BET surface areas of MOP, MOP-AC and MOP-ACZ were found to be 12.60, 4.10 and 45.96 m2/g, respectively. The experimental data were analyzed by Langmuir, Freundlich and Temkin adsorption isotherm models. Equilibrium data fitted well with the Langmuir isotherm with a maximum monolayer adsorption capacity of 20.14 mg g-1. The rates of adsorption were found to conform to the pseudo-second-order kinetics with a good correlation. The results indicate that the M. oleifera activated carbon could be employed as a low-cost alternative to commercial activated carbon in the removal of BPA from water.
Microplastic (MP) is an emerging contaminant of concern due to its abundance in the environment. Wastewater treatment plant (WWTP) can be considered as one of the main sources of microplastics in freshwater due to its inefficiency in the complete removal of small MPs. In this study, a column-based MP removal which could serve as a tertiary treatment in WWTPs is evaluated using granular activated carbon (GAC) as adsorbent/filter media, eliminating clogging problems commonly caused by powder form activated carbon (PAC). The GAC is characterized via N2 adsorption-desorption isotherm, field emission scanning electron microscopy, and contact angle measurement to determine the influence of its properties on MP removal efficiency. MPs (40-48 μm) removal up to 95.5% was observed with 0.2 g/L MP, which is the lowest concentration tested in this work, but still higher than commonly used MP concentration in other studies. The performance is reduced with further increase in MP concentration (up to 1.0 g/L), but increasing the GAC bed length from 7.5 to 17.5 cm could lead to better removal efficiencies. MP particles are immobilized by the GAC predominantly by filtration process by being entangled with small GAC particles/chips or stuck between the GAC particles. MPs are insignificantly removed by adsorption process through entrapment in GAC porous structure or attachment onto the GAC surface.