Algal biomass is known as a promising sustainable feedstock for the production of biofuels and other valuable products. However, since last decade, massive amount of interests have turned to converting algal biomass into biochar. Due to their high nutrient content and ion-exchange capacity, algal biochars can be used as soil amendment for agriculture purposes or adsorbents in wastewater treatment for the removal of organic or inorganic pollutants. This review describes the conventional (e.g., slow and microwave-assisted pyrolysis) and newly developed (e.g., hydrothermal carbonization and torrefaction) methods used for the synthesis of algae-based biochars. The characterization of algal biochar and a comparison between algal biochar with biochar produced from other feedstocks are also presented. This review aims to provide updated information on the development of algal biochar in terms of the production methods and the characterization of its physical and chemical properties to justify and to expand their potential applications.
A one-step self-sustained carbonization of coconut shell biomass, carried out in a brick reactor at a relatively low temperature of 300-500°C, successfully produced a biochar-derived adsorbent with 308 m2/g surface area, 2 nm pore diameter, and 0.15 cm3/g total pore volume. The coconut shell biochar qualifies as a nano-adsorbent, supported by scanning electron microscope images, which showed well-developed nano-pores on the surface of the biochar structure, even though there was no separate activation process. This is the first report whereby coconut shell can be converted to biochar-derived nano-adsorbent at a low carbonization temperature, without the need of the activation process. This is superior to previous reports on biochar produced from oil palm empty fruit bunch.
Microwave-steam activation (MSA), an innovative pyrolysis approach combining the use of microwave heating and steam activation, was investigated for its potential production of high grade activated carbon (AC) from waste palm shell (WPS) for methylene blue removal. MSA was performed via pyrolytic carbonization of WPS to produce biochar as the first step followed by steam activation of the biochar using microwave heating to form AC. Optimum yield and adsorption efficiency of methylene blue were obtained using response surface methodology involving several key process parameters. The resulting AC was characterized for its porous characteristics, surface morphology, proximate analysis and elemental compositions. MSA provided a high activation temperature above 500 °C with short process time of 15 min and rapid heating rate (≤150 °C/min). The results from optimization showed that one gram of AC produced from steam activation under 10 min of microwave heating at 550 °C can remove up to 38.5 mg of methylene blue. The AC showed a high and uniform surface porosity consisting high fixed carbon (73 wt%), micropore and BET surface area of 763.1 and 570.8 m2/g respectively, hence suggesting the great potential of MSA as a promising approach to produce high grade adsorbent for dye removal.
Engineered biochar is increasingly regarded as a cost-effective and eco-friendly peroxymonosulfate (PMS) activator. Herein, biochar doped with nitrogen and sulfur moieties was prepared by pyrolysis of wood shavings and doping precursor. The doping precursor consists of either urea, thiourea or 1:1 w/w mixture of urea and thiourea (denoted as NSB-U, NSB-T and NSB-UT, respectively). The physicochemical properties of the NSBs were extensively characterized, revealing that they are of noncrystalline carbon with porous structure. The NSBs were employed as PMS activator to degrade organic pollutants particularly methylene blue (MB). It was found that NSB-UT exhibited higher MB removal rate with kapp = 0.202 min-1 due to its relatively high surface area and favorable intrinsic surface moieties (combination of graphitic N and thiophenic S). The effects of catalyst loading, PMS dosage and initial pH were evaluated. Positive enhancement of the MB removal rate can be obtained by carefully increasing the catalyst loading or PMS dosage. Meanwhile, the MB removal rate is greatly influenced by pH due to electrostatic interactions and pH dependent reactions. The NSB-UT can be reused for several cycles to some extent and its catalytic activity can be restored by thermal treatment. Based on the radical scavenger study and XPS analysis, the nonradical pathway facilitated by the graphitic N and thiophenic S active sites are revealed to be the dominant reaction pathway. Overall, the results of this study show that engineered biochar derived from locally available biowaste can be transformed into PMS activator for environmental applications.
The environmental footprints of H2productionviacatalytic gasification of wheat straw using straw-derived biochar catalysts were examined. The functional unit of 1 kg of H2was adopted in the system boundaries, which includes 5 processes namely biomass collection and pre-treatment units (P1), biochar catalyst preparation using fast pyrolysis unit (P2), two-stage pyrolysis-gasification unit (P3), products separation unit (P4), and H2distribution to downstream plants (P5). Based on the life-cycle assessment, the hot spots in this process were identified, the sequence was as follows: P4 > P2 > P1 > P3 > P5. The end-point impacts score for the process was found to be 93.4017 mPt. From benchmarking analysis, the proposed straw-derived biochar catalyst was capable of offering almost similar catalytic performance with other metal-based catalysts with a lower environmental impact.
The emission of sulphur dioxide (SO2) gas from power plants and factories to the atmosphere has been an environmental challenge globally. Thus, there is a great interest to control the SO2 gas emission economically and effectively. This study aims to use and convert abundantly available oil palm fiber (OPF) biomass into an adsorbent to adsorb SO2 gas. The preparation of OPF biochar and activated biochar was optimised using the Response Surface Methodology (RSM) based on selected parameters (i.e., pyrolysis temperature, heating rate, holding time, activation temperature, activation time and CO2 flowrate). The best adsorbent was found to be the OPF activated biochar (OPFAB) compared to OPF biochar. OPFAB prepared at 753 °C for 73 min of activation time with 497 ml/min of CO2 flow yields the best adsorption capacity (33.09 mg/g) of SO2. Meanwhile, OPF pyrolysed at 450 °C of heating temperature, 12 °C/min of heating rate and 98 min of holding time yield adsorption capacity at 18.62 mg/g. Various characterisations were performed to investigate the properties and mechanism of the SO2 adsorption process. Thermal regeneration shows the possibilities for the spent adsorbent to be recycled. The findings imply OPFAB as a promising adsorbent for SO2 adsorption.
Over the past decade, there has been a surge of interest in using char (hydrochar or biochar) derived from biomass as persulfate (PS, either peroxymonosulfate or peroxydisulfate) activator for anthropogenic pollutants removal. While extensive investigation showed that char could be used as a PS activator, its sustainability over prolonged application is equivocal. This review provides an assessment of the knowledge gap related to the sustainability of char as a PS activator. The desirable char properties for PS activation are identified, include the high specific surface area and favorable surface chemistry. Various synthesis strategies to obtain the desirable properties during biomass pre-treatment, hydrochar and biochar synthesis, and char post-treatment are discussed. Thereafter, factors related to the sustainability of employing char as a PS activator for anthropogenic pollutants removal are critically evaluated. Among the critical factors include performance uncertainty, competing adsorption process, char stability during PS activation, biomass precursor variation, scalability, and toxic components in char. Finally, some potential research directions are provided. Fulfilling the sustainability factors will provide opportunity to employ char as an economical and efficient catalyst for sustainable environmental remediation.
This work investigates the performances of coconut shell waste-based activated carbon (CSWAC) adsorption in batch studies for removal of ammoniacal nitrogen (NH3-N) and refractory pollutants (as indicated by decreasing COD concentration) from landfill leachate. To valorize unused resources, coconut shell, recovered and recycled from agricultural waste, was converted into activated carbon, which can be used for leachate treatment. The ozonation of the CSWAC was conducted to enhance its removal performance for target pollutants. The adsorption mechanisms of refractory pollutants by the adsorbent are proposed. Perspectives on nutrient recovery technologies from landfill leachate from the view-points of downstream processing are presented. Their removal efficiencies for both recalcitrant compounds and ammoniacal nitrogen were compared to those of other techniques reported in previous work. It is found that the ozonated CSWAC substantially removed COD (i.e. 76%) as well as NH3-N (i.e. 75%), as compared to the CSWAC without pretreatment (i.e. COD: 44%; NH3-N: 51%) with NH3-N and COD concentrations of 2750 and 8500 mg/L, respectively. This reveals the need of ozonation for the adsorbent to improve its performance for the removal of COD and NH3-N at optimized reactions: 30 g/L of CSWAC, pH 8, 200 rpm of shaking speed and 20 min of reaction time. Nevertheless, treatment of the leachate samples using the ozonated CSWAC alone was still unable to result in treated effluents that could meet the COD and NH3-N discharge standards below 200 and 5 mg/L, respectively, set by legislative requirements. This reveals that another treatment is necessary to be undertaken to comply with the requirement of their effluent limit.
Pot experiments were conducted to investigate the influence of biochar addition and the mechanisms that alleviate Cd stress in the growth of tobacco plant. Cadmium showed an inhibitory effect on tobacco growth at different post-transplantation times, and this increased with the increase in soil Cd concentration. The growth index decreased by more than 10%, and the photosynthetic pigment and photosynthetic characteristics of the tobacco leaf were significantly reduced, and the antioxidant enzyme activity was enhanced. Application of biochar effectively alleviated the inhibitory effect of Cd on tobacco growth, and the alleviation effect of treatments is more significant to the plants with a higher Cd concentration. The contents of chlorophyll a, chlorophyll b, and carotenoids in the leaves of tobacco plants treated with biochar increased by 9.99%, 12.58%, and 10.32%, respectively, after 60 days of transplantation. The photosynthetic characteristics index of the net photosynthetic rate increased by 11.48%, stomatal conductance increased by 11.44%, and intercellular carbon dioxide concentration decreased to 0.92. Based on the treatments, during the growth period, the antioxidant enzyme activities of tobacco leaves comprising catalase, peroxidase, superoxide dismutase, and malondialdehyde increased by 7.62%, 10.41%, 10.58%, and 12.57%, respectively, after the application of biochar. Our results show that biochar containing functional groups can effectively reduce the effect of Cd stress by intensifying the adsorption or passivation of Cd in the soil, thereby, significantly reducing the Cd content in plant leaves, and providing a theoretical basis and method to alleviate soil Cd pollution and effect soil remediation.
This study focuses on the biochar formation and torrefaction performance of sugarcane bagasse, and they are predicted using the bilinear interpolation (BLI), inverse distance weighting (IDW) interpolation, and regression analysis. It is found that the biomass torrefied at 275°C for 60min or at 300°C for 30min or longer is appropriate to produce biochar as alternative fuel to coal with low carbon footprint, but the energy yield from the torrefaction at 300°C is too low. From the biochar yield, enhancement factor of HHV, and energy yield, the results suggest that the three methods are all feasible for predicting the performance, especially for the enhancement factor. The power parameter of unity in the IDW method provides the best predictions and the error is below 5%. The second order in regression analysis gives a more reasonable approach than the first order, and is recommended for the predictions.
Fruit peel, an abundant waste, represents a potential bio-resource to be converted into useful materials instead of being dumped in landfill sites. Palm oil mill effluent (POME) is a harmful waste that should also be treated before it can safely be released to the environment. In this study, pyrolysis of banana and orange peels was performed under different temperatures to produce biochar that was then examined as adsorbent in POME treatment. The pyrolysis generated 30.7-47.7 wt% yield of a dark biochar over a temperature ranging between 400 and 500 °C. The biochar contained no sulphur and possessed a hard texture, low volatile content (≤34 wt%), and high amounts of fixed carbon (≥72 wt%), showing durability in terms of high resistance to chemical reactions such as oxidation. The biochar showed a surface area of 105 m2/g and a porous structure containing mesopores, indicating its potential to provide many adsorption sites for use as an adsorbent. The use of the biochar as adsorbent to treat the POME showed a removal efficiency of up to 57% in reducing the concentration of biochemical oxygen demand (BOD), chemical oxygen demand COD, total suspended solid (TSS) and oil and grease (O&G) of POME to an acceptable level below the discharge standard. Our results indicate that pyrolysis shows promise as a technique to transform banana and orange peel into value-added biochar for use as adsorbent to treat POME. The recovery of biochar from fruit waste also shows advantage over traditional landfill approaches in disposing this waste.
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.
Biochar production from invasive species biomass discarded as waste was studied in a fixed bed reactor pyrolysis system under different temperature conditions for value-added applications. Prior to pyrolysis, the biomass feedstock was characterized by proximate, ultimate, and heating value analyses, while the biomass decomposition behavior was examined by thermogravimetric analysis. The heating values of the feedstock biomass ranged from 18.65 to 20.65 MJ/kg, whereas the volatile matter, fixed carbon, and ash content were 61.54-72.04 wt %, 19.27-26.61 wt % and 1.51-1.86 wt %, respectively. The elemental composition of carbon, hydrogen, and oxygen in the samples was reported to be in the range of 47.41-48.47 wt %, 5.50-5.88 wt % and 46.10-45.18 wt %, respectively, while the nitrogen and sulphur content in the biomass samples were at very low concentrations, making it more useful for valorization from environmental aspects. The biochar yields were reported in the range of 45.36-58.35 wt %, 28.63-44.38 wt % and 22.68-29.42 wt % at a pyrolysis temperature of 400 °C, 500 °C, and 600 °C, respectively. The biochars were characterized from ultimate analysis, heating value, energy densification ratio, energy yield, pH, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy and energy dispersive X-ray spectrometry (SEM and EDX), to evaluate their potential for value-added applications. The carbon content, heating value, energy densification ratio, and the porosity of the biochars improved with the increase in pyrolysis temperature, while the energy yield, hydrogen, oxygen, and nitrogen content of the biochars decreased. This study revealed the potential of the valorization of underutilized discarded biomass of invasive species via a pyrolysis process to produce biochar for value-added applications.
This study provides insight into the decolorization strategy for crude glycerol obtained from biodiesel production using waste cooking oil as raw material. A sequential procedure that includes physico-chemical treatment and adsorption using activated carbon from oil palm biomass was investigated. The results evidenced decolorization and enrichment of glycerol go hand in hand during the treatment, achieving >89% color removal and > 98% increase in glycerol content, turning the glycerol into a clear (colorless) solution. This is attributed to the complete removal of methanol, free fatty acids, and triglycerides, as well as 85% removal of water, and 93% removal of potassium. Properties of the resultant glycerol met the quality standard of BS 2621:1979. The economic aspects of the proposed methods are examined to fully construct a predesign budgetary estimation according to chemical engineering principles. The starting capital is proportionate to the number of physical assets to acquire where both entail a considerable cost at USD 13,200. Having the benefit of sizeable scale production, it reasonably reduces the operating cost per unit product. As productivity sets at 33 m3 per annum, the annual operating costs amount to USD 79,902 in glycerol decolorization. This is translatable to USD 5.38 per liter glycerol, which is ~69% lower compared to using commercial activated carbon.
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.
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.
Bamboo is the fastest-growing plant and is abundant in Malaysia. It is employed as a starting material for activated carbon production and evaluated for its potential in CO2 capture. A single-stage phosphoric acid (H3PO4) activation is adopted by varying the concentrations of H3PO4 between 50 and 70 wt.% at a constant temperature and holding time of 500°C and 120 min, respectively. The bamboo-based activated carbons are characterized in terms of product yield, surface area, and porosity, as well as surface chemistry properties. Referring to the experimental findings, the prepared activated carbons have BET surface area of >1000 m2 g-1, which implies the effectiveness of the single-stage H3PO4 activation. Furthermore, the prepared activated carbon via 50 wt.% H3PO4 activation shows the highest BET surface area and carbon dioxide (CO2) adsorption capacity of 1.45 mmol g-1 at 25°C/1 bar and 9.0 mmol g-1 at 25°C/30 bar. With respect to both the characterization analysis and CO2 adsorption performance, it is concluded that bamboo waste conversion to activated carbon through H3PO4 activation method is indeed promising.
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.
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.