Palm ash, an agriculture waste residue from palm-oil industry in Malaysia, was investigated as a replacement for the current expensive methods of removing direct blue 71 dye from an aqueous solution. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption. Equilibrium data fitted well with Freundlich model in the range of 50-600mg/L. The equilibrium adsorption capacity of the palm ash was determined with the Langmuir equation and found to be 400.01mg dye per gram adsorbent at 30 degrees C. The rates of adsorption were found to conform to the pseudo-second-order kinetics with good correlation. The results indicate that the palm ash could be employed as a low-cost alternative to commercial activated carbon.
The current research investigates synthesis of methyl esters by transesterification of waste cooking oil in a heterogeneous system, using barium meliorated construction site waste marble as solid base catalyst. The pretreated catalyst was calcined at 830 °C for 4h prior to its activity test to obtained solid oxide characterized by scanning electron microscopy/energy dispersive spectroscopy, BET surface area and pore size measurement. It was found that the as prepared catalyst has large pores which contributed to its high activity in transesterification reaction. The methyl ester yield of 88% was obtained when the methanol/oil molar ratio was 9:1, reaction temperature at 65 °C, reaction time 3h and catalyst/oil mass ratio of 3.0 wt.%. The catalyst can be reused over three cycles, offer low operating conditions, reduce energy consumption and waste generation in the production of biodiesel.
The preparation of tamarind fruit seed granular activated carbon (TSAC) by microwave induced chemical activation for the adsorptive treatment of semi-aerobic landfill leachate has been attempted. The chemical and physical properties of TSAC were examined. A series of column tests were performed to determine the breakthrough characteristics, by varying the operational parameters, hydraulic loading rate (5-20 mL/min) and adsorbent bed height (15-21 cm). Ammonical nitrogen and chemical oxygen demand (COD), which provide a prerequisite insight into the prediction of leachate quality was quantified. Results illustrated an encouraging performance for the adsorptive removal of ammonical nitrogen and COD, with the highest bed capacity of 84.69 and 55.09 mg/g respectively, at the hydraulic loading rate of 5 mL/min and adsorbent bed height of 21 cm. The dynamic adsorption behavior was satisfactory described by the Thomas and Yoon-Nelson models. The findings demonstrated the applicability of TSAC for the adsorptive treatment of landfill leachate.
The combustion characteristics of Karanj fruit hulls char (KFH-char) was investigated with thermogravimetry analysis (TGA). The TGA outlined the char combustion thermographs at a different heating rate and isoconversional methods expressed the combustion kinetics. The Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) methods authenticated the char average activation energy at 62.13 and 68.53kJ/mol respectively, enough to derive the char to burnout. However, the Coats-Redfern method verified the char combustion via complex multi-step mechanism; the second stage mechanism has 135kJ/mol average activation energy. The TGA thermographs and kinetic parameters revealed the adequacy of the KFH-char as fuel substrate than its precursor, Karanj fruit hulls (KFH).
The synthesis of fatty acid methyl ester (FAME) from the high- and low-acid-content feedstock of crude palm oil (CPO) and karanj oil (KO) was conducted over CaO-La2O3-Al2O3 mixed-oxide catalyst. Various reaction parameters were investigated using a batch reactor to identify the best reaction condition that results in the highest FAME yield for each type of oil. The transesterification of CPO resulted in a 97.81% FAME yield with the process conditions of 170°C reaction temperature, 15:1 DMC-to-CPO molar ratio, 180min reaction time, and 10wt.% catalyst loading. The transesterification of KO resulted in a 96.77% FAME yield with the conditions of 150°C reaction temperature, 9:1 DMC-to-KO molar ratio, 180min reaction time, and 5wt.% catalyst loading. The properties of both products met the ASTM D6751 and EN 14214 standard requirements. The above results showed that the CaO-La2O3-Al2O3 mixed-oxide catalyst was suitable for high- and low-acid-content vegetable oil.
This study examined the combustion profile and kinetics of hydrochar produced from hydrothermal carbonisation (HTC) of Karanj fruit hulls (KFH). The HTC-KFH hydrochar combustion kinetics was investigated at 5, 10, and 20°C/min by thermogravimetric analysis. The kinetics model, Kissinger-Akahira-Sunose revealed the combustion kinetics parameters for the extent of conversion from 0.1 to 0.8; the activation energy varies from 114 to 67 kJ/mol respectively. The hydrochar combustion followed multi-steps kinetics; the Coats-Redfern models predicted the activation energies and pre-exponential constants for the hydrochar combustion zones. The diffusion models are the effective mechanism in the second and third zone.
This study investigated the catalytic co-pyrolysis of sugarcane bagasse (SCB) and waste high-density polyethylene (HDPE) over faujasite-type zeolite derived from electric arc furnace slag (FAU-EAFS) in a fixed-bed reactor. The effects of reaction temperature, catalyst-to-feedstock ratio, and HDPE-to-SCB ratio on product fractional yields and chemical compositions were discussed. The co-pyrolysis of SCB and HDPE over FAU-EAFS increased the liquid yield and enhanced the quality of bio-oil. The maximum bio-oil (68.56 wt%) and hydrocarbon yield (74.55%) with minimum yield of oxygenated compounds (acid = 0.57% and ester = 0.67%) were achieved under the optimum experimental conditions of catalyst-to-feedstock ratio of 1:6, HDPE-to-SCB ratio of 40:60, and temperature of 500 °C. The oil produced by catalytic co-pyrolysis had higher calorific value than the oil produced by the pyrolysis of SCB alone.
The adsorption of residue oil from palm oil mill effluent (POME) using chitosan powder and flake has been investigated. POME contains about 2g/l of residue oil, which has to be treated efficiently before it can be discharged. Experiments were carried out as a function of different initial concentrations of residue oil, weight dosage, contact time and pH of chitosan in powder and flake form to obtain the optimum conditions for the adsorption of residue oil from POME. The powder form of chitosan exhibited a greater rate compared to the flake type. The results obtained showed that chitosan powder, at a dosage of 0.5g/l, 15min of contact time and a pH value of 5.0, presented the most suitable conditions for the adsorption of residue oil from POME. The adsorption process performed almost 99% of residue oil removal from POME. Equilibrium studies have been carried out to determine the capacity of chitosan for the adsorption of residue oil from POME using the optimum conditions from the flocculation at different initial concentrations of residue oil. Langmuir and Freundlich adsorption models were applied to describe the experimental isotherms and isotherm constants. Equilibrium data fitted very well with the Freundlich model. The pseudo first- and second-order kinetic models and intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The experimental data fitted well with the second-order kinetic model, which indicates that the chemical sorption is the rate-limiting step, i.e. chemisorption between residue oil and chitosan. The significant uptake of residue oil on chitosan was further proved by BET surface area analysis and SEM micrographs.
Cross-linked chitosan/sepiolite composite was prepared from sepiolite clay and chitosan, and was cross-linked using epichlorohydrin. Among the various weight ratio percentage of chitosan and sepiolite clay composites, CS50SP50 was selected as the best adsorbent for both methylene blue (MB) and reactive orange 16 (RO 16). At an optimum adsorbent dosage of 0.2g/100mL, the effects of initial dye concentration (25-400mg/L) and pH (3-11) on MB and RO 16 adsorption onto CS50SP50 composite were studied. Monolayer adsorption capacities of CS50SP50 composite for MB and RO 16 were 40.986mg/g and 190.965mg/g, respectively at 30°C. Freundlich, Langmuir and Temkin isotherms applied on the adsorption data for both the dyes reveal that data fitted best for Freundlich model. For both the dyes pseudo-second-order kinetics were found to describe the adsorption process better than pseudo-first-order kinetics. The adsorption capacity of CS50SP50 composite for both the dyes was found better compared to previous studies thus making it potentially low-cost adsorbent for removal of both cationic and reactive dyes.
Fabrication of an immobilized cross-linked chitosan-epichlorohydrine thin film (CLCETF) onto glass plate for adsorption of reactive orange 16 (RO16) dye was successfully studied using the direct casting technique. Adsorption experiments were performed as a function of contact time, initial dye concentration (25mg/L to 350mg/L), and pH (3-11). The adsorption isotherm followed the Langmuir model. The adsorption capacity of CLECTF for RO16 was 356.50mg/g at 27±2°C. The kinetics closely followed the pseudo-second-order model. Results supported the potential use of an immobilized CLECTF as effective adsorbent for the treatment of reactive dye without using filtration process.
Silica-alumina catalyst was prepared and used in the catalytic fast pyrolysis of durian rind in a drop-type two-stage reactor. The effects of catalytic temperature (400 °C-600 °C) and catalyst-to-durian rind ratio (1:30-3:30) were evaluated. Bio-oil yield was increased with increased catalytic temperature due to considerable dehydration process, but it was reduced with high catalyst loading due to the overcracking of organics into light gases. Silica-alumina catalyst possessed good selectivity and the products changed according to the temperature. The major components in bio-oil were hydrocarbons, furan derivatives, and aromatic compounds at 400 °C, 500 °C, and 600 °C, respectively. The hydrogen and carbon contents of bio-oil were reduced with high catalyst loading due to the overcracking of organics, and the deoxygenation process became unfavorable. The silica-alumina catalyst worked well in catalytic fast pyrolysis of durian rind, and the condition may be adjusted based on the desired products.
Cross-linked beads of activated oil palm ash zeolite/chitosan (Z-AC/C) composite were prepared through the hydrothermal treatment of NaOH activated oil palm ash followed by beading with chitosan. The effects of initial dye concentration (50-400mg/L), temperature (30°C-50°C) and pH (3-13) on batch adsorption of methylene blue (MB) and acid blue 29 (AB29) were studied. Adsorption of both dyes was better described by Pseudo-second-order kinetics and Freundlich isotherm model. The maximum adsorption capacities of Z-AC/C were 151.51, 169.49, and 199.20mg/g for MB and 212.76, 238.09, and 270.27mg/g for AB29 at 30°C, 40°C, and 50°C, respectively.
Co-pyrolysis of biomass with abundantly available materials could be an economical method for production of bio-fuels. However, elimination of oxygenated compounds poses a considerable challenge. Catalytic co-pyrolysis is another potential technique for upgrading bio-oils for application as liquid fuels in standard engines. This technique promotes the production of high-quality bio-oil through acid catalyzed reduction of oxygenated compounds and mutagenic polyaromatic hydrocarbons. This work aims to review and summarize research progress on co-pyrolysis and catalytic co-pyrolysis, as well as their benefits on enhancement of bio-oils derived from biomass. This review focuses on the potential of plastic wastes and coal materials as co-feed in co-pyrolysis to produce valuable liquid fuel. This paper also proposes future directions for using this technique to obtain high yields of bio-oils.
Catalysts prepared from industrial wastes rich in Fe, Ca, Si, and Al were used in catalytic upgrading of pyrolysis vapour derived from durian shell and their effect on product yield and properties were compared. With same silica-to-alumina ratio, catalyst prepared from oil palm ash (AS-OPA) with lower Fe and Ca contents gave higher liquid yield (8.32 wt%) with alcohols (28.90%), hydrocarbons (46.00%), and nitrogen-containing compounds (21.46%) while catalyst prepared from electric arc furnace slag (AS-EAF) with higher Fe and Ca contents produced lower liquid yield (50.21 wt%) with high amount of esters (25.80%) and hydrocarbons (72.82%). The presence of AS-OPA and AS-EAF catalysts enhanced deoxygenation degree of bio-oil to 81.13% and 85.49%, respectively. The catalytic performance of AS-EAF at different temperatures (400-600 °C) and AS-EAF/durian shell ratios (1:30, 2:30, 3:30) was investigated. Increasing catalytic temperature enhanced production of bio-oil, reduced oxygenates and enhanced formation of esters. The liquid yield and yield of esters decreased with increasing catalyst loading. Hydrocarbons (mainly neopentane) were the major chemical compounds found in bio-oil produced over AS-EAF. Besides that, AS-EAF showed good deoxygenation performance with highest selectivity of hydrocarbons at 500 °C and AS-EAF/durian shell ratio of 2:30. Catalytic fast pyrolysis of durian shell using waste-derived catalysts is an effective waste management strategy as the bio-oil produced can be a potential alternative source of energy or chemical feedstocks.
The pyrolysis of oil palm mesocarp fiber (OPMF) was catalyzed with a steel slag-derived zeolite (FAU-SL) in a slow-heating fixed-bed reactor at 450 °C, 550 °C, and 600 °C. The catalytic pyrolysis of OPMF produced a maximum yield of 47 wt% bio-oil at 550 °C, and the crude pyrolysis vapor (CPV) of this process yielded crude pyrolysis oil with broad distribution of bulky oxygenated organic compounds. The bio-oil composition produced at 550 °C contained mainly light and stable acid-rich carbonyls at a relative abundance of 48.02% peak area and phenolic compounds at 12.03% peak area. The FAU-SL high mesoporosity and strong surface acidity caused the conversion of the bulky CPV molecules into mostly light acid-rich carbonyls and aromatics through secondary reactions. The secondary reactions mechanisms facilitated by FAU-SL reduced the distribution of the organic compounds in the bio-oil to mostly acid-rich carbonyls and aromatic in contrast to other common zeolite.
Oil palm mesocarp fiber (OPMF) and palm frond (PF) were respectively devolatilized by pyrolysis to OPMF-oil and PF-oil bio-oils and biochars, OPMF-char and PF-char in a slow-heating fixed-bed reactor. In particular, the OPMF-oil and PF-oil were produced to a maximum yield of 48wt% and 47wt% bio-oils at 550°C and 600°C, respectively. The high heating values (HHVs) of OPMF-oil and PF-oil were respectively found to be 23MJ/kg and 21MJ/kg, whereas 24.84MJ/kg and 24.15MJ/kg were for the corresponding biochar. The HHVs of the bio-oils and biochars are associated with low O/C ratios to be higher than those of the corresponding biomass. The Fourier transform infrared spectra and peak area ratios highlighted the effect of pyrolysis temperatures on the bio-oil compositions. The bio-oils are pervaded with numerous oxygenated carbonyl and aromatic compounds as suitable feedstocks for renewable fuels and chemicals.
Durian shell (DS) was pyrolyzed in a drop-type fixed-bed reactor to study the physicochemical properties of the products. The experiment was carried out with different particle sizes (up to 5mm) and reaction temperatures (250-650°C). The highest bio-oil yield was obtained at 650°C (57.45wt%) with DS size of 1-2mm. The elemental composition and higher heating value of the feedstock, bio-oil (650°C), and bio-char (650°C) were determined and compared. The compositions of product gases were determined via gas chromatography with thermal conductivity detector. The chemical composition of bio-oil was analyzed by gas chromatography-mass spectrometry. The bio-oil produced at lower temperature yields more alcohols, whereas the bio-oil produced at higher temperature contains more aromatics and carbonyls. Bio-oil has potential to be used as liquid fuel or fine chemical precursor after further upgrading. The results further showed the potential of bio-char as a solid fuel.
The removal of toxic herbicide from wastewater is challenging due to the availability of suitable adsorbents. The Langsat empty fruit bunch is an agricultural waste and was used in this study as a cheap precursor to produce activated carbon for the adsorption of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) at different initial concentrations ranging from 50 to 400 mg/L. The produced Langsat empty fruit bunch activated carbon (LEFBAC) was mesoporous and had high surface area of 1065.65 m(2)/g with different active functional groups. The effect of shaking time, temperature and pH on 2,4-D removal were investigated using the batch technique. The adsorption capacity of 2,4-D by LEFBAC was decreased with increase in pH of solution whereas adsorption capacity increased with temperature. The adsorption data was well described by Langmuir isotherm followed by removal capacity of 261.2 mg/g at 30 °C. The results from this work showed that LEFBAC can be used as outstanding material for anionic herbicide uptake from wastewater.
The potential of Mg(x)Co(2-)(x)O(2) as heterogeneous reusable catalyst in transesterification of palm oil to methyl ester was investigated. The catalyst was prepared via co-precipitation of the metal hydroxides at different Mg-Co ratios. Mg(1.7)Co(0.3)O(2) catalyst was more active than Mg(0.3)Co(1.7)O(2) in the transesterification of palm oil with methanol. The catalysts calcined at temperature 300 °C for 4 h resulted in highly active oxides and the highest transesterification of 90% was achieved at methanol/oil molar ratio of 9:1, catalyst loading of 5.00 wt.%, reaction temperature of 150 °C and reaction time of 2 h. The catalyst could easily be removed from reaction mixture, but showed 50% decrease in activity when reused due to leaching of active sites.
The effects of three preparation variables: CO(2) activation temperature, CO(2) activation time and KOH:char impregnation ratio (IR) on the 2,4,6-trichlorophenol (2,4,6-TCP) uptake and carbon yield of the activated carbon prepared from oil palm empty fruit bunch (EFB) were investigated. Based on the central composite design, two quadratic models were developed to correlate the three preparation variables to the two responses. The activated carbon preparation conditions were optimized using response surface methodology by maximizing both the 2,4,6-TCP uptake and activated carbon yield within the ranges studied. The optimum conditions for preparing activated carbon from EFB for adsorption of 2,4,6-TCP were found as follows: CO(2) activation temperature of 814 degrees C, CO(2) activation time of 1.9h and IR of 2.8, which resulted in 168.89 mg/g of 2,4,6-TCP uptake and 17.96% of activated carbon yield. The experimental results obtained agreed satisfactorily with the model predictions. The activated carbon prepared under optimum conditions was mesoporous with BET surface area of 1141 m(2)/g, total pore volume of 0.6 cm(3)/g and average pore diameter of 2.5 nm. The surface morphology and functional groups of the activated carbon were respectively determined from the scanning electron microscopy and Fourier transform infrared analysis.