Oxygenated fuel additives can be produced by acetylation of glycerol. A 91% glycerol conversion with a selectivity of 38%, 28% and 34% for mono-, di- and triacetyl glyceride, respectively, was achieved at 120 °C and 3 h of reaction time in the presence of a catalyst derived from activated carbon (AC) treated with sulfuric acid at 85 °C for 4h to introduce acidic functionalities to its surface. The unique catalytic activity of the catalyst, AC-SA5, was attributed to the presence of sulfur containing functional groups on the AC surface, which enhanced the surface interaction between the glycerol molecule and acyl group of the acetic acid. The catalyst was reused in up to four consecutive batch runs and no significant decline of its initial activity was observed. The conversion and selectivity variation during the acetylation is attributed to the reaction time, reaction temperature, catalyst loading and glycerol to acetic acid molar ratio.
Fatty acid methyl ester was produced from used vegetable cooking oil using Mg(1-)(x) Zn(1+)(x)O(2) solid catalyst and the performance monitored in terms of ester content obtained. Used vegetable cooking oil was employed to reduce operation cost of biodiesel. The significant operating parameters which affect the overall yield of the process were studied. The highest ester content, 80%, was achieved with the catalyst during 4h 15 min reaction at 188°C with methanol to oil ratio of 9:1 and catalyst loading of 2.55 wt% oil. Also, transesterification of virgin oil gave higher yield with the heterogeneous catalyst and showed high selectivity towards ester production. The used vegetable cooking oil did not require any rigorous pretreatment. Catalyst stability was examined and there was no leaching of the active components, and its performance was as good at the fourth as at the first cycle.
In this study, methyl ester (ME) was produced by transesterification of palm oil (CPO) (cooking grade) using activated carbon supported calcium oxide as a solid base catalyst (CaO/AC). Response surface methodology (RSM) based on central composite design (CCD) was used to optimize the effect of reaction time, molar ratio of methanol to oil, reaction temperature and catalyst amount on the transesterification process. The optimum condition for CPO transesterification to methyl ester was obtained at 5.5 wt.% catalyst amount, 190°C temperature, 15:1 methanol to oil molar ratio and 1 h 21 min reaction time. At the optimum condition, the ME content was 80.98%, which is well within the predicted value of the model. Catalyst regeneration studies indicate that the catalyst performance is sustained after two cycles.
This study investigated the adsorption potential of oil palm shell-based activated carbon to remove 2,4,6-trichlorophenol from aqueous solution using fixed-bed adsorption column. The effects of 2,4,6-trichlorophenol inlet concentration, feed flow rate and activated carbon bed height on the breakthrough characteristics of the adsorption system were determined. The regeneration efficiency of the oil palm shell-based activated carbon was evaluated using ethanol desorption technique. Through ethanol desorption, 96.25% of the adsorption sites could be recovered from the regenerated 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.
An active heterogeneous Al2O3 modified MgZnO (MgZnAlO) catalyst was prepared and the catalytic activity was investigated for the transesterification of different vegetable oils (refined palm oil, waste cooking palm oil, palm kernel oil and coconut oil) with methanol to produce biodiesel. The catalyst was characterized by using X-ray diffraction, Fourier transform infrared spectra, thermo gravimetric and differential thermal analysis to ascertain its versatility. Effects of important reaction parameters such as methanol to oil molar ratio, catalyst dosage, reaction temperature and reaction time on oil conversion were examined. Within the range of studied variability, the suitable transesterification conditions (methanol/oil ratio 16:1, catalyst loading 3.32 wt.%, reaction time 6h, temperature 182°C), the oil conversion of 98% could be achieved with reference to coconut oil in a single stage. The catalyst can be easily recovered and reused for five cycles without significant deactivation.
In this work, preparation of granular activated carbon from oil palm biodiesel solid residue, oil palm shell (PSAC) by microwave assisted KOH activation has been attempted. The physical and chemical properties of PSAC were characterized using scanning electron microscopy, volumetric adsorption analyzer and elemental analysis. The adsorption behavior was examined by performing batch adsorption experiments using methylene blue as dye model compound. Equilibrium data were simulated using the Langmuir, Freundlich and Temkin isotherm models. Kinetic modeling was fitted to the pseudo-first-order, pseudo-second-order and Elovich kinetic models, while the adsorption mechanism was determined using the intraparticle diffusion and Boyd equations. The result was satisfactory fitted to the Langmuir isotherm model with a monolayer adsorption capacity of 343.94mg/g at 30°C. The findings support the potential of oil palm shell for preparation of high surface area activated carbon by microwave assisted KOH activation.
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.
A high-performance porous biochar adsorbent prepared by facile thermal pyrolysis of seaweed (Gelidiella acerosa) is reported. The textural characteristics of the prepared seaweed biochar (SWBC) and the performance in the adsorption of methylene blue (MB) dye were evaluated. The batch experiment for the adsorption of MB was conducted under different parameters, such as temperature, pH, and initial concentration of MB in the range of 25-400 mg/L. The developed SWBC exhibited a relatively high surface area, average pore size, and pore volume of 926.39 m2/g, 2.45 nm, and 0.57 cm3/g, respectively. The high surface area and pristine mineral constituents of the biochar promoted a high adsorption capacity of 512.67 mg/g of MB at 30 °C. The adsorption isotherm and kinetics data best fitted the Langmuir and pseudo-second-order equations. The results indicate that SWBC is efficient for MB adsorption and could be a potential adsorbent for wastewater treatment.
Cephalexin (CFX) antibiotic, a potent pharmaceutical water pollutant, was efficiently removed by activated carbon (AC) derived from a single-step pyrolysis of phosphoric acid-activated chitin. Experimental conditions such as temperature, CFX initial concentration, and solution pH were screened in batch adsorption. Phosphoric acid activation of chitin and subsequent pyrolysis tailored the Brunauer-Emmett-Teller surface area, total pore volume, and average pore diameter to 1199.02 m2/g, 0.641 cm3/g, and 21.37 Å, respectively. The Langmuir isotherm adequately described the equilibrium data for CFX adsorption on chitin-AC, with an R2 of 0.99 and a monolayer capacity of 245.19 mg/g at 50 °C. Chitin-AC showed higher adsorption capacity compared with other ACs derived from industrial and agricultural precursors. When activated by phosphoric acid, chitin-AC featured functional multi-sites for vast antibiotic adsorption treatment. Overall, chitin-AC could be a promising adsorbent for removal of CFX.
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.
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.
In this work, a human hair-derived high surface area porous carbon material (HHC) was prepared using potassium hydroxide activation. The morphology and textural properties of the HHC structure, along with its adsorption performance for tetracycline (TC) antibiotics, were evaluated. HHC showed a high surface area of 1505.11m(2)/g and 68.34% microporosity. The effects of most important variables, such as initial concentration (25-355mg/L), solution pH (3-13), and temperatures (30-50°C), on the HHC adsorption performance were investigated. Isotherm data analysis revealed the favorable application of the Langmuir model, with maximum TC uptakes of 128.52, 162.62, and 210.18mg/g at 30, 40, and 50°C, respectively. The experimental data of TC uptakes versus time were analyzed efficiently using a pseudo-first order model. Porous HHC could be an efficient adsorbent for eliminating antibiotic pollutants in wastewater.
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.
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.