The synthesis of fatty acid ethyl esters (FAEEs) by a two-step in situ (reactive) esterification/transesterification from Jatropha curcas L. (JCL) seeds using microwave system has been investigated. Free fatty acid was reduced from 14% to less than 1% in the first step using H2SO4 as acid catalyst after 35 min of microwave irradiation heating. The organic phase in the first step was subjected to a second reaction by adding 5 N KOH in ethanol as the basic catalyst. Response surface methodology (RSM) based on central composite design (CCD) was utilized to design the experiments and analyze the influence of process variables (particles seed size, time of irradiation, agitation speed and catalyst loading) on conversion of triglycerides (TGs) in the second step. The highest triglycerides conversion to fatty acid ethyl esters (FAEEs) was 97.29% at the optimum conditions:<0.5mm seed size, 12.21 min irradiation time, 8.15 ml KOH catalyst loading and 331.52 rpm agitation speed in the 110 W microwave power system.
Anaerobic digestion for palm oil mill effluent (POME) is widely known for its potential in biogass production. In this study, the potential of using cattle manure for biogas production in complete mix anaerobic bioreactor was investigated using POME at unregulated pH and temperature. Two identical bioreactors were used in this study; namely R1 and R2 fed with cattle manure without and with POME as inoculum, respectively. Both bioreactors were allowed for five days to run in batch mode followed by semi continuous operations at HRT of 20 days. R2 produced 41% methane content compared to 18% produced in R1. A better COD percentage reduction of 45% was found in R2 which was operated with POME as inoculum compared to R1 with 35%. These results indicated that POME as inoculum has an influence on the start-up time and the rate of biogas produced.This findings will help in waste reduction.
Biofuels are viewed as promising alternatives to conventional fossil fuels because they have the potential to eliminate major environmental problems created by fossil fuels. Among the still developing biofuel technologies, biodiesel production from algae offers a greater prospect for large-scale practical use, as algae are capable of producing much more yield than other biofuels. While research on algae-based biofuel is still in its developing stage, extensive work on laboratory- and pilot-scale algae harvesting systems with promising prospects has been reported. This paper presented a discussion of the literature review on recent advances in algae separation, harvesting and drying for biofuel production. The review and discussion focus on destabilization of algae, algae harvesting technologies and algae drying processes. Challenges and prospects of algae harvesting are also outlined.
Optimization of thermo-alkaline disintegration of sewage sludge for enhanced biogas yield was carried out using response surface methodology (RSM) and Box-Behnken design of experiment. The individual linear and quadratic effects as well as the interactive effects of temperature, NaOH concentration and time on the degree of disintegration were investigated. The optimum degree of disintegration achieved was 61.45% at 88.50 °C, 2.29 M NaOH (24.23%w/w total solids) and 21 min retention time. Linear and quadratic effects of temperature are most significant in affecting the degree of disintegration. The coefficient of determination (R(2)) of 99.5% confirms that the model used in predicting the degree of disintegration process has a very good fitness with the experimental variables. The disintegrated sludge increased the biogas yield by 36%v/v compared to non-disintegrated sludge. The RSM with Box-Behnken design is an effective tool in predicting the optimum degree of disintegration of sewage sludge for increased biogas yield.
The synthesis of oxygenated fuel additives via solvent freebase-catalyzed etherification of glycerol is reported. The products of glycerol etherification arediglycerol (DG) and triglycerol (TG) with DG being the favorable one. The catalytic activity of different homogeneous alkali catalysts (LiOH, NaOH, KOH and Na(2)CO(3)) was investigated during the glycerol etherification process. LiOH exhibited an excellent catalytic activity during this reaction, indicated by the complete glycerol conversion with a corresponding selectivity of 33% toward DG. The best reaction conditions were a reaction temperature of 240°C, a catalyst/glycerol mass ratio of 0.02 and a reaction time of 6h. The influences of various reaction variables such as nature of the catalyst, catalyst loading, reaction time and reaction temperature on glycerol etherification were elucidated. Industrially, the findings attained in this study might contribute towards promoting the biodiesel industry through utilization of its by-products.
The importance of bioethanol currently has increased tremendously as it can reduce the total dependency on fossil-fuels, especially gasoline, in the transportation sector. In this study, Ceiba pentandra (kapok fiber) was introduced as a new resource for bioethanol production. The results of chemical composition analysis showed that the cellulose (alpha- and beta-) contents were 50.7%. The glucose composition of the fiber was 59.8%. The high glucose content indicated that kapok fiber is a potential substrate for bioethanol production. However, without a pretreatment, the kapok fiber only yielded 0.8% of reducing sugar by enzymatic hydrolysis. Thus, it is necessary to pre-treat the kapok fiber prior to hydrolysis. Taking into account environmentally friendliness, only simple pretreatments with minimum chemical or energy consumption was considered. It was interesting to see that by adopting merely water, acid and alkaline pretreatments, the yield of reducing sugar was increased to 39.1%, 85.2% and >100%, respectively.
Oil palm empty fruit bunch pellets were subjected to pyrolysis in a multimode microwave (MW) system (1 kW and 2.45 GHz frequency) with and without the MW absorber, activated carbon. The ratio of biomass to MW absorber not only affected the temperature profiles of the EFB but also pyrolysis products such as bio-oil, char, and gas. The highest bio-oil yield of about 21 wt.% was obtained with 25% MW absorber. The bio-oil consisted of phenolic compounds of about 60-70 area% as detected by GC-MS and confirmed by FT-IR analysis. Ball lightning (plasma arc) occurred due to residual palm oil in the EFB biomass without using an MW absorber. The bio-char can be utilized as potential alternative fuel because of its heating value (25 MJ/kg).
Novel heterogeneous catalysts from calcium oxide (CaO)/calcined calcium carbonate (CaCO(3)) loaded onto different palm oil mill boiler ashes were synthesised and used in the transesterification of crude palm oil (CPO) with methanol to yield biodiesel. Catalyst preparation parameters including the type of ash support, the weight percentage of CaO and calcined CaCO(3) loadings, as well as the calcination temperature of CaCO(3) were optimised. The catalyst prepared by loading of 15 wt% calcined CaCO(3) at a fixed temperature of 800°C on fly ash exhibited a maximum oil conversion of 94.48%. Thermogravimetric analysis (TGA) revealed that the CaCO(3) was transformed into CaO at 770°C and interacted well with the ash support, whereas rich CaO, Al(2)O(3) and SiO(2) were identified in the composition using X-ray diffraction (XRD). The fine morphology size (<5 μm) and high surface area (1.719 m(2)/g) of the fly ash-based catalyst rendered it the highest catalytic activity.
Thermophilic treatment of palm oil mill effluent (POME) was studied in a novel integrated anaerobic-aerobic bioreactor (IAAB). The IAAB was subjected to a program of steady-state operation over a range of organic loading rate (OLR)s, up to 30 g COD/L day in order to evaluate its treatment capacity. The thermophilic IAAB achieved high chemical oxygen demand (COD), biochemical oxygen demand (BOD) and total suspended solids (TSS) removal efficiencies of more than 99% for OLR up to 18.5 g COD/L day. High methane yield of 0.32 LCH(4) (STP)/g COD(removed) with compliance of the final treated effluent to the discharge limit were achieved. This is higher than that of the mesophilic system due to the higher maximum specific growth rate (μ(max)) of the thermophilic microorganisms. Besides, coupling the model of Grau second order model (anaerobic system) with the model of Monod (aerobic system) will completely define the IAAB system.
Transesterification reaction of Jatropha curcas oil with methanol was carried out in the presence of ash generated from Palm empty fruit bunch (EFB) in a heterogeneous catalyzed process. The ash was doped with KOH by impregnation to achieve a potassium level of 20 wt.%. Under optimum conditions for the EFB-catalyzed (65 °C, oil/methanol ratio of 15, 90 min, 20 wt.% EFB ash catalyst) and the KOH-EFB-catalyzed reactions (65 °C, oil/methanol ratio of 15, 45 min, 15 wt.% of KOH doped EFB ash), biodiesel (>98%) with specifications higher than those stipulated by European biodiesel quality standard EN 14214 was obtained.
This study was undertaken to investigate the effects of different nitrate concentrations in culture medium on oil content and fatty acid composition of Chlorella vulgaris (UMT-M1) and Chlorella sorokiniana (KS-MB2). Results showed that both species produced significant higher (p<0.05) oil content at nitrate ranging from 0.18 to 0.66 mM with C. vulgaris produced 10.20-11.34% dw, while C. sorokiniana produced 15.44-17.32% dw. The major fatty acids detected include C16:0, C18:0, C18:1, C18:2 and C18:3. It is interesting to note that both species displayed differentially regulated fatty acid accumulation patterns in response to nitrate treatments at early stationary growth phase. Their potential use for biodiesel application could be enhanced by exploring the concept of binary blending of the two microalgae oils using developed mathematical equations to calculate the oil mass blending ratio and simultaneously estimated the weight percentage (wt.%) of desirable fatty acid compositions.
Fatty acid methyl esters (FAME) were produced from palm oil using eggshell modified with magnesium and potassium nitrates to form a composite, low-cost heterogeneous catalyst for transesterification. The catalyst, prepared by the combination of impregnation/co-precipitation was calcined at 830 °C for 4 h. Transesterification was conducted at a constant temperature of 65 °C in a batch reactor. Design of experiment (DOE) was used to optimize the reaction parameters, and the conditions that gave highest yield of FAME (85.8%) was 5.35 wt.% catalyst loading at 4.5 h with 16:1 methanol/oil molar ratio. The results revealed that eggshell, a solid waste, can be utilized as low-cost catalyst after modification with magnesium and potassium nitrates for biodiesel production.
The catalytic cracking of waste cooking palm oil to biofuel was studied over different types of nano-crystalline zeolite catalysts in a fixed bed reactor. The effect of reaction temperature (400-500 °C), catalyst-to-oil ratio (6-14) and catalyst pore size of different nanocrystalline zeolites (0.54-0.80 nm) were studied over the conversion of waste cooking palm oil, yields of Organic Liquid Product (OLP) and gasoline fraction in the OLP following central composite design (CCD). The response surface methodology was used to determine the optimum value of the operating variables for maximum conversion as well as maximum yield of OLP and gasoline fraction, respectively. The optimum reaction temperature of 458 °C with oil/catalyst ratio=6 over the nanocrystalline zeolite Y with pore size of 0.67 nm gave 86.4 wt% oil conversion, 46.5 wt% OLP yield and 33.5 wt% gasoline fraction yield, respectively. The experimental results were in agreement with the simulated values within an experimental error of less than 5%.
An industrial grade acidic crude palm oil (ACPO) pre-treatment process was carried out using ethanesulfonic acid (ESA) as a catalyst in the esterification reaction. ESA was used in different dosages to reduce free fatty acid (FFA) to a minimum level for the second stage of biodiesel production via alkaline transesterification reaction. Different process operating conditions were optimized such as ESA dosage (0.25-3.5% wt/wt), methanol to ACPO molar ratio (1:1-20:1), reaction temperature (40-70 °C), and reaction time (3-150 min). This study revealed the potential use of abundant quantities of ACPO from oil palm mills for biodiesel production. The lab scale results showed the effectiveness of the pre-treatment process using ESA catalyst. Three consecutive catalyst recycling runs were achieved without significant degradation in its performance. Second and third reuse runs needed more reaction time to achieve the target level of FFA content. Esterification and transesterification using ESA and KOH respectively is proposed for biodiesel industrial scale production. The produced biodiesel meets the international standards specifications for biodiesel fuel (EN 14214 and ASTM D6751).
This study identifies the potential greenhouse gas (GHG) reductions, which can be achieved by optimizing the use of residues in the life cycle of palm oil derived biodiesel. This is done through compilation of data on existing and prospective treatment technologies as well as practical experiments on methane potentials from empty fruit bunches. Methane capture from the anaerobic digestion of palm oil mill effluent was found to result in the highest GHG reductions. Among the solid residues, energy extraction from shells was found to constitute the biggest GHG savings per ton of residue, whereas energy extraction from empty fruit bunches was found to be the most significant in the biodiesel production life cycle. All the studied waste treatment technologies performed significantly better than the conventional practices and with dedicated efforts of optimized use in the palm oil industry, the production of palm oil derived biodiesel can be almost carbon neutral.
Preparation of activated carbon has been attempted using KOH as activating agent by microwave heating from biodiesel industry solid residue, oil palm empty fruit bunch (EFBAC). The significance of chemical impregnation ratio (IR), microwave power and activation time on the properties of activated carbon were investigated. The optimum condition has been identified at the IR of 1.0, microwave power of 600 W and activation time of 7 min. EFBAC was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and nitrogen adsorption isotherm. The surface chemistry was examined by zeta potential measurement, determination of surface acidity/basicity, while the adsorptive property was quantified using methylene blue as dye model compound. The optimum conditions resulted in activated carbon with a monolayer adsorption capacity of 395.30 mg/g and carbon yield of 73.78%, while the BET surface area and total pore volume were corresponding to 1372 m2/g and 0.76 cm3/g, respectively.
Biohydrogen is regarded as an attractive future clean energy carrier due to its high energy content and environmental-friendly conversion. It has the potential for renewable biofuel to replace current hydrogen production which rely heavily on fossil fuels. While biohydrogen production is still in the early stage of development, there have been a variety of laboratory- and pilot-scale systems developed with promising potential. This work presents a review of advances in bioreactor and bioprocess design for biohydrogen production. The state-of-the art of biohydrogen production is discussed emphasizing on production pathways, factors affecting biohydrogen production, as well as bioreactor configuration and operation. Challenges and prospects of biohydrogen production are also outlined.
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.
In this study, biodiesel was produced from sludge palm oil (SPO) using tolune-4-sulfonic monohydrate acid (PTSA) as an acid catalyst in different dosages in the presence of methanol to convert free fatty acid (FFA) to fatty acid methyl ester (FAME), followed by a transesterification process using an alkaline catalyst. In the first step, acid catalyzed esterification reduced the high FFA content of SPO to less than 2% with the different dosages of PTSA. The optimum conditions for pretreatment process by esterification were 0.75% (w/w) dosage of PTSA to SPO, 10:1 M ratio, 60 °C temperature, 60 min reaction time and 400 rpm stirrer speed. The highest yield of biodiesel after transesterification and purification processes was 76.62% with 0.07% FFA and 96% ester content. The biodiesel produced was favorable as compared to EN 14214 and ASTM 6751 standard. This study shows a potential exploitation of SPO as a new feedstock for the production of biodiesel.
In order to characterize enzyme activity and stability corresponding to temperature effects, thermodynamic studies on commercial immobilized lipase have been carried out via enzymatic transesterification. An optimum temperature of 40 degrees C was obtained in the reaction. The decreasing reaction rates beyond the optimum temperature indicated the occurrence of reversible enzyme deactivation. Thermodynamic studies on lipase denaturation exhibited a first-order kinetics pattern, with considerable stability through time shown by the lipase as well. The activation and deactivation energies were 22.15 kJ mol(-1) and 45.18 kJ mol(-1), respectively, implying more energy was required for the irreversible denaturation of the enzyme to occur. At water content of 0.42%, the initial reaction rate and FAME yield displayed optimum values of 3.317 g/L min and 98%, respectively.