In this study, a binary mixture of petroleum coke and palm kernel shell had been investigated as potential starting materials for activated carbon production. Single-stage potassium carbonate (K2CO3) activation under nitrogen (N2) atmosphere was adopted in this research study. Effect of several operating parameters that included the impregnation ratio (1-3 wt./wt.), activation temperature (600-800 °C), and dwell time (1-2 hrs) were analyzed by using the Box-Behnken experimental design. Influence of these parameters towards activated carbon yield (Y1) and carbon dioxide (CO2) adsorption capacity at an atmospheric condition (Y2) were investigated. The optimum conditions for the activated carbon production were attained at impregnation ratio of 1.75:1, activation temperature of 680 °C, and dwell time of 1 h, with its corresponding Y1 and Y2 is 56.2 wt.% and 2.3991 mmol/g, respectively. Physicochemical properties of the pristine materials and synthesized activated carbon at the optimum conditions were analyzed in terms of their decomposition behavior, surface morphology, elemental composition, and textural characteristics. The study revealed that the blend of petroleum coke and palm kernel shell can be effectively used as the activated carbon precursors, and the experimental findings demonstrated comparable CO2 adsorption performance with commercial activated carbon as well as that in literatures.
The feasibility of biomass-based activated carbons has received a huge attention due to their excellent characteristics such as inexpensiveness, good adsorption behaviour and potential to reduce a strong dependency towards non-renewable precursors. Therefore, in this research work, eco-friendly activated carbon from palm kernel shell that has been produced from one-stage physical activation by using the Box-Behnken design of Response Surface Methodology is highlighted. The effect of three input parameters-temperature, dwell time and gas flow rate-towards product yield and carbon dioxide (CO2) uptake at room temperature and atmospheric pressure are studied. Model accuracy has been evaluated through the ANOVA analysis and lack-of-fit test. Accordingly, the optimum condition in synthesising the activated carbon with adequate CO2 adsorption capacity of 2.13 mmol/g and product yield of 25.15 wt% is found at a temperature of 850 °C, holding time of 60 min and CO2 flow rate of 450 cm3/min. The synthesised activated carbon has been characterised by diverse analytical instruments including thermogravimetric analyser, scanning electron microscope, as well as N2 adsorption-desorption isotherm. The characterisation analysis indicates that the synthesised activated carbon has higher textural characteristics and porosity, together with better thermal stability and carbon content as compared to pristine palm kernel shell. Activated carbon production via one-step activation approach is economical since its carbon yield is within the industrial target, whereas CO2 uptake is comparable to the synthesised activated carbon from conventional dual-stage activation, commercial activated carbon and other published data from literature.
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 mathematical model describing chemical kinetics of transesterification of palm-based methyl esters with trimethylolpropane has been developed. The model was developed by utilizing nonlinear regression method, which is an efficient and powerful way to determine rate constants for both forward and reverse reactions. A comparison with previous study which excludes the reverse reactions was made. The model was based on the reverse mechanism of transesterification reactions and describes concentration changes of trimethylolpropane, monoesters and diesters production. The developed model was validated against data from the literature. The reaction rate constants were determined using MATLAB version 7.2 and the ratios of rate constants obtained were well in agreement with those reported in the literature. A good correlation between model simulations and experimental data was observed. It was proven that both methods were able to predict the rate constants with plausible accuracy.
Biomass wastes produced from oil palm mills and plantations include empty fruit bunches (EFBs), shells, fibers, trunks, and oil palm fronds (OPF). EFBs and shells are partially utilized as boiler fuel while the rest of the biomass materials like OPF have not been utilized for energy generation. No previous study has been reported on gasification of oil palm fronds (OPF) biomass for the production of fuel gas. In this paper, the effect of moisture content of fuel and reactor temperature on downdraft gasification of OPF was experimentally investigated using a lab scale gasifier of capacity 50 kW. In addition, results obtained from equilibrium model of gasification that was developed for facilitating the prediction of syngas composition are compared with experimental data. Comparison of simulation results for predicting calorific value of syngas with the experimental results showed a satisfactory agreement with a mean error of 0.1 MJ/Nm³. For a biomass moisture content of 29%, the resulting calorific value for the syngas was found to be only 2.63 MJ/Nm³, as compared to nearly double (4.95 MJ/Nm³) for biomass moisture content of 22%. A calorific value as high as 5.57 MJ/Nm³ was recorded for higher oxidation zone temperature values.
Recently, a great attention has been paid to advanced microwave technology that can be used to markedly enhance the biodiesel production process. Ceiba pentandra Seed Oil containing high free fatty acids (FFA) was utilized as a non-edible feedstock for biodiesel production. Microwave-assisted esterification pretreatment was conducted to reduce the FFA content for promoting a high-quality product in the next step. At optimum condition, the conversion was achieved 94.43% using 2wt% of sulfuric acid as catalyst where as 20.83% conversion was attained without catalyst. The kinetics of this esterification reaction was also studied to determine the influence of factors on the rate of reaction and reaction mechanisms. The results indicated that microwave-assisted esterification was of endothermic second-order reaction with the activation energy of 53.717kJ/mol.
The energy demand in Malaysia has shown a dramatic increase over the last few years: with natural gas and coal being the primary contributors. Nevertheless, due to declining in fossil fuel reserves coupled with negative environmental impacts, shifting to sustainable renewable energy for meeting the future energy demand is recommended. Since Malaysia is rich with natural resources, utilization of biomass energy (bioenergy/biofuel) as the alternative energy is promising to be further explored. Therefore, this review paper intents to discuss the current scenario of different types of biomass energy in Malaysia along with the up-to-date local biomass energy-related environmental policy (from 2016 onwards). In addition, challenges and barriers for large-scale implementation of the biomass energy in Malaysia are to be discussed. Overall, this review paper is interesting as it can assist in promoting the biomass utilization as energy source, and to ensure the future growth of biomass energy market in the country along with its effective implementation while alleviating poor disposal problem and to create job employment opportunities. Furthermore, a collective effort to expand potential biomass feedstocks, apart from oil palm, should be emphasized to encourage the renewable energy production diversification in the nation.
Recently, rubber seed oil (RSO) has been considered as a promising potential oil source for biodiesel production. However, RSO is a non-edible feedstock with a significant high free fatty acid (FFA) content which has an adverse impact on the process of biodiesel production. In this study, ultrasonic-assisted esterification process was conducted as a pre-treatment step to reduce the high FFA content of RSO from 40.14% to 0.75%. Response surface methodology (RSM) using central composite design (CCD) was applied to the design of experiments (DOE) and the optimization of esterification process. The result showed that methanol to oil molar ratio was the most influential factor for FFA reduction whereas the effect of amount of catalyst and the reaction were both insignificant. The kinetic study revealed that the activation energy and the frequency factor of the process are 52.577kJ/mol and 3.53×108min-1, respectively.
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.
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.
This study evaluated the potential of bioflocculant production from Aspergillus niger using palm oil mill effluent (POME) as carbon source. The bioflocculant named PM-5 produced by A. niger showed a good flocculating capability and flocculating rate of 76.8% to kaolin suspension could be achieved at 60 h of culture time. Glutamic acid was the most favorable nitrogen source for A. niger in bioflocculant production at pH 6 and temperature 35 °C. The chemical composition of purified PM-5 was mainly carbohydrate and protein with 66.8% and 31.4%, respectively. Results showed the novel bioflocculant (PM-5) had high potential to treat river water from colloids and 63% of turbidity removal with the present of Ca(2+) ion.
Biodiesel from Jatropha curcas L. seed is conventionally produced via a two-step method: extraction of oil and subsequent esterification/transesterification to fatty acid methyl esters (FAME), commonly known as biodiesel. Contrarily, in this study, a single step in situ extraction, esterification and transesterification (collectively known as reactive extraction) of J. curcas L. seed to biodiesel, was investigated and optimized. Design of experiments (DOE) was used to study the effect of various process parameters on the yield of FAME. The process parameters studied include reaction temperature (30-60 degrees C), methanol to seed ratio (5-20 mL/g), catalyst loading (5-30 wt %), and reaction time (1-24 h). The optimum reaction condition was then obtained by using response surface methodology (RSM) coupled with central composite design (CCD). Results showed that an optimum biodiesel yield of 98.1% can be obtained under the following reaction conditions: reaction temperature of 60 degrees C, methanol to seed ratio of 10.5 mL/g, 21.8 wt % of H(2)SO(4), and reaction period of 10 h.
The main objective of this paper is to find the optimum operating condition to upgrade the EFB-derived pyrolysis oil (bio-oil) to liquid fuel, mainly gasoline using Taguchi Method. From the analysis that has been done, it is found that the optimum operating condition for heterogeneous catalytic cracking process is at 400 degrees C, 15min of reaction time using 30g of catalyst weight where operating at this condition produced the highest yield of gasoline fraction which is 91.67 wt.%. This observation proves that EFB-derived pyrolysis oil could be upgraded via heterogeneous catalytic cracking to produce gasoline.
Hydrodeoxygenation is one of the promising technologies for the transformation of triglycerides into long-chain hydrocarbon fuel commonly known as green diesel. The hydrodeoxygenation (HDO) of rubber seed oil into diesel range (C15-C18) hydrocarbon over non-sulphided bimetallic (Ni-Mo/γ-Al2O3 solid catalysts were studied. The catalysts were synthesized via wet impregnation method as well as sonochemical method. The synthesized catalysts were subjected to characterization methods including FESEM coupled with EDX, XRD, BET, TEM, XPS, NH3-TPD, CO-chemisorption and H2-TPR in order to investigate the effects of ultrasound irradiations on physicochemical properties of the catalyst. All the catalysts were tested for HDO reaction at 350 °C, 35 bar, H2/oil 1000 N (cm3/cm3) and WHSV = 1 h-1 in fixed bed tubular reactor. The catalyst prepared via sonochemical method showed comparatively higher specific surface area, particles in nano-size and uniform distribution of particle on the external surface of the support, higher crystallinity and lower reduction temperature as well as higher concentration of Mo4+ deoxygenating metal species. These physicochemical properties improved the catalytic activity compared to conventionally synthesized catalyst for HDO of rubber seed oil. The catalytic performance of sonochemically synthesized Ni-Mo/γ-Al2O3 catalyst (80.87%) was higher than the catalyst prepared via wet impregnation method (63.3%). The sonochemically synthesized Ni-Mo/γ-Al2O3 catalyst is found to be active, produces 80.87 wt% of diesel range hydrocarbons, and it gives high selectivity for Pentadecane (18.7 wt%), Hexadecane (16.65 wt%), Heptadecane (24.45 wt%) and Octadecane (21.0 wt%). The product distribution revealed that the deoxygenation reaction pathway was preferred. Higher conversion and higher HDO yield in this study are associated mainly with the change in concentration ratio between oxidation states of molybdenum (Mo4+, Mo5+, and Mo6+) on the external surface of the catalyst due to ultrasound irradiation during the synthesis process. Consequently, the application of sonochemically synthesized non-sulphided catalysts favored mainly hydrodeoxygenation of diesel range hydrocarbon.
The CO2 capture capacity and cyclic stability of calcium oxide (CaO) prepared from cockle shells (CS) were enhanced by incorporating rice husk (RH) and binder through wet-mixing method. The cyclic reaction of calcination and carbonation was demonstrated using thermal gravimetric analyzer (TGA) which the calcination was performed in a pure N2 environment at 850 °C for 20 min and carbonation at 650 °C for 30 min in 20 vol% of CO2 in N2. The analysis using x-ray fluorescence (XRF) identified silica (Si) as the major elements in the sorbents. The RH-added sorbents also contained several types of metal elements such as which was a key factor to minimize the sintering of the sorbent during the cyclic reaction and contributed to higher CO2 capture capacity. The presence of various morphologies also associated with the improvement of the synthesized sorbents performance. The highest initial CO2 capture capacity was exhibited by CS+10%RH sorbent, which was 12% higher than the RH-free sorbent (CS). However, sorbents with the higher RH loading amount such as 40 and 50 wt% were preferred to maintain high capture capacity when the sorbents were regenerated and extended to the cyclic reaction. The sorbents also demonstrated the lowest average sorption decay, which suggested the most stable sorbent for cyclic-reaction. Once regenerated, the capture capacity of the RH-added sorbent was further increased by 12% when clay was added into the sorbent. Overall, the metal elements in RH and clay were possibly the key factor that enhances the performance of CaO prepared from CS, particularly for cyclic CO2 capture. Graphical abstract Cyclic calcination and carbonation reaction.
The present work analyzes the effect of antioxidants on engine combustion performance of a multi-cylinder diesel engine fueled with PB30 and PB50 (30 and 50 vol.% palm biodiesel (PB)). Four antioxidants namely N,N'-diphenyl-1,4-phenylenediamine (DPPD), N-phenyl-1,4-phenylenediamine (NPPD), 2(3)-tert-Butyl-4-methoxyphenol (BHA), and 2-tert-butylbenzene-1,4-diol (TBHQ) were added at concentrations of 1000 and 2000 ppm to PB30 and PB50. TBHQ showed the highest activity in increasing oxidation stability in both PB30 and PB50 followed by BHA, DPPD, and NPPD respectively, without any negative effect on physical properties. Compared to diesel fuel, PB blends showed 4.61-6.45% lower brake power (BP), 5.90-8.69% higher brake specific fuel consumption (BSFC), 9.64-11.43% higher maximum in cylinder pressure, and 7.76-12.51% higher NO emissions. Carbon monoxide (CO), hydrocarbon (HC), and smoke opacity were reduced by 36.78-43.56%, 44.12-58.21%, and 42.59-63.94%, respectively, than diesel fuel. The start of combustion angles (SOC) of PB blends was - 13.2 to - 15.6 °CA BTDC, but the combustion delays were 5.4-7.8 °CA short compared to diesel fuel which were - 10 °CA BTDC and 11°CA respectively. Antioxidant fuels of PB showed higher BP (1.81-5.32%), CO (8.41-24.60%), and HC (13.51-37.35%) with lower BSFC (1.67-7.68%), NO (4.32-11.53%), maximum in cylinder pressure (2.33-4.91%) and peak heat release rates (HRR) (3.25-11.41%) than baseline fuel of PB. Similar SOC of - 13 to - 14 °CA BTDC was observed for PB blended fuels and antioxidants. It can be concluded that antioxidants' addition is effective in increasing the oxidation stability and in controlling the NOx emissions of palm biodiesel fuelled diesel engine.
The abundance of food waste across the globe has called for the mitigation and reduction of these discarded wastes. Herein, the potential of biochar derived from food waste is unquestionable as it provides a sustainable way of utilizing the abundance of available biomass, as well as an effective way of preserving the ecosystem through the reduction of concerning environmental issues. This review focuses on the food waste-based biochar as advanced electrode materials in the energy storage devices. Efforts have been made to present and discuss the current exploration of the food waste utilization, along with the biochar production technologies through thermochemical conversion, including combustion, gasification, and pyrolysis method. Finding its limitation in literatures, discussion on the food waste-based biochar fabrication method as the electrode materials is elaborated, alongside the current food waste-based biochar that has been explored in the energy application thus far. Towards the end, the outlook and perspective on the further development of food waste-based biochar have been outlined.
Pretreatment of the high free fatty acid rubber seed oil (RSO) via esterification reaction has been investigated by using a pilot scale hydrodynamic cavitation (HC) reactor. Four newly designed orifice plate geometries are studied. Cavities are induced by assisted double diaphragm pump in the range of 1-3.5 bar inlet pressure. An optimised plate with 21 holes of 1mm diameter and inlet pressure of 3 bar resulted in RSO acid value reduction from 72.36 to 2.64 mg KOH/g within 30 min of reaction time. Reaction parameters have been optimised by using response surface methodology and found as methanol to oil ratio of 6:1, catalyst concentration of 8 wt%, reaction time of 30 min and reaction temperature of 55°C. The reaction time and esterified efficiency of HC was three fold shorter and four fold higher than mechanical stirring. This makes the HC process more environmental friendly.
The aim of this work was to characterize the natural low transition temperature mixtures (LTTMs) as promising green solvents for biomass pretreatment with the critical characteristics of cheap, biodegradable and renewable, which overcome the limitations of ionic liquids (ILs). The LTTMs were derived from inexpensive commercially available hydrogen bond acceptor (HBA) and l-malic acid as the hydrogen bond donor (HBD) in distinct molar ratios of starting materials and water. The peaks involved in the H-bonding shifted and became broader for the OH groups. The thermal properties of the LTTMs were not affected by water while the biopolymers solubility capacity of LTTMs was improved with the increased molar ratio of water and treatment temperature. The pretreatment of oil palm biomass was consistence with the screening on solubility of biopolymers. This work provides a cost-effective alternative to utilize microwave hydrothermal extracted green solvents such as malic acid from natural fruits and plants.
The aim of this study was to understand the influence of catalyst in thermal degradation behavior of rice husk (RH) in catalytic fast pyrolysis (CFP) process. An iso-conversional Kissinger kinetic model was introduced into this study to understand the activation energy (EA), pre-exponential value (A), Enthalpy (ΔH), Entropy (ΔS) and Gibb's energy (ΔG) of non-catalytic fast pyrolysis (NCFP) and CFP of RH. The study revealed that the addition of natural zeolite catalyst enhanced the rate of devolatilization and decomposition of RH associated with lowest EA value (153.10 kJ/mol) compared to other NCFP and CFP using nickel catalyst. Lastly, an uncertainty estimation was applied on the best fit non-linear regression model (MNLR) to identify the explanatory variables. The finding showed that it had the highest probability to obtain 73.8-74.0% mass loss in CFP of rice husk using natural zeolite catalyst.