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.
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.
Bifunctional heterogeneous catalysts have a great potential to overcome the shortcomings of homogeneous and enzymatic catalysts and simplify the biodiesel production processes using low-grade, high-free-fatty-acid feedstock. In this study, we developed ZrO2-based bifunctional heterogeneous catalysts for simultaneous esterification and transesterification of microalgae to biodiesel. To avoid the disadvantage of the low surface area of ZrO2, the catalysts were prepared via a surfactant-assisted sol-gel method, followed by hydrothermal treatments. The response surface methodology central composite design was employed to investigate various factors, like the surfactant/Zr molar ratio, pH, aging time, and temperature on the ZrO2 surface area. The data were statistically analyzed to predict the optimal combination of factors, and further experiments were conducted for verification. Bi2O3 was supported on ZrO2 via the incipient wetness impregnation method. The catalysts were characterized by a variety of techniques, which disclosed that the surfactant-assisted ZrO2 nanoparticles possess higher surface area, better acid-base properties, and well-formed pore structures than bare ZrO2. The highest yield of fatty acid methyl esters (73.21%) was achieved using Bi2O3/ZrO2(CTAB), and the catalytic activity of the developed catalysts was linearly correlated with the total densities of the acidic and basic sites. The mechanism of the simultaneous reactions was also discussed.
Torrefaction of oil palm empty fruit bunches (EFB) under combustion gas atmosphere was conducted in a batch reactor at 473, 523 and 573K in order to investigate the effect of real combustion gas on torrefaction behavior. The solid mass yield of torrefaction in combustion gas was smaller than that of torrefaction in nitrogen. This may be attributed to the decomposition enhancement effect by oxygen and carbon dioxide in combustion gas. Under combustion gas atmosphere, the solid yield for torrefaction of EFB became smaller as the temperature increased. The representative products of combustion gas torrefaction were carbon dioxide and carbon monoxide (gas phase) and water, phenol and acetic acid (liquid phase). By comparing torrefaction in combustion gas with torrefaction in nitrogen gas, it was found that combustion gas can be utilized as torrefaction gas to save energy and inert gas.
In this study, the flocculation behavior and mechanism of a cation-independent bioflocculant IH-7 produced by Aspergillus flavus were investigated. Results showed 91.6% was the lowest flocculating rate recorded by IH-7 (0.5 mg L(-1)) at pH range 4-8. Moreover, IH-7 showed better flocculation performance than polyaluminum chloride (PAC) at a wide range of flocculant concentration (0.06-25 mg L(-1)), temperature (5-45 °C) and salinity (10-60% w/w). The current study found that cation addition did not significantly enhance the flocculating rate and IH-7 is a positively charged bioflocculant. These findings suggest that charge neutralization is the main flocculation mechanism of IH-7 bioflocculant. IH-7 was significantly used to flocculate different types of suspended solids such as activated carbons, kaolin clays, soil solids and yeast cells.
In this study, a novel method for the production of biodiesel under mild conditions using fine particles of sodium methoxide formed in dimethyl carbonate (DMC) is proposed. Biodiesel is generally produced from vegetable oils by the transesterification of triglycerides with methanol. However, this reaction produces glycerol as a byproduct, and raw materials are not effectively utilized. Transesterification with DMC has recently been studied because glycerol is not formed in the process. Although solid-state sodium methoxide has been reported to be inactive for this reaction, the catalytic activity dramatically increased with the preparation of fine catalyst powders by crystallization. The transesterification of canola oil with DMC was studied using this catalyst for the preparation of biodiesel. A conversion greater than 96% was obtained at 65°C for 2h with a 3:1M ratio of DMC and oil and 2.0 wt% catalyst.
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.
Natural hydro-low-transition-temperature mixtures (NH-LTTMs) tend to be the most favorable next-generation green solvents for biomass pretreatment, as they are cheap and environmental friendly. The amount of water bound into the NH-LTTMs greatly affected their thermal stability, whereby the highest thermal stability was observed with the water content of 7.6 wt%. It is worth noting that, the highest molar transition energy of NH-LTTMs (47.57 kcal mol-1), which indicated the highest solubility, was optimized with the molar ratio of hydrogen bond donor (HBD)-hydrogen bond acceptor (HBA)-water (2:4:3) at a temperature of 60 °C. Hydrogen bonding networks of the NH-LTTMs, which led to the dissolution of biomass, were confirmed by the alteration in the peaks of the involved bonds and resonance signal to lower field through FTIR and 1H NMR spectra, respectively. The components evidenced in high-resolution mass spectra of extracted lignin showed its high potential to be valorized into useful fuels and chemicals.
This work aimed to develop an efficient microwave-hydrothermal (MH) extraction of malic acid from abundant natural cactus as hydrogen bond donor (HBD) whereby the concentration was optimized using response surface methodology. The ideal process conditions were found to be at a solvent-to-feed ratio of 0.008, 120°C and 20min with 1.0g of oxidant, H2O2. Next generation environment-friendly solvents, low transition temperature mixtures (LTTMs) were synthesized from cactus malic acid with choline chloride (ChCl) and monosodium glutamate (MSG) as hydrogen bond acceptors (HBAs). The hydrogen-bonding interactions between the starting materials were determined. The efficiency of the LTTMs in removing lignin from oil palm biomass residues, empty fruit bunch (EFB) was also evaluated. The removal of amorphous hemicellulose and lignin after the pretreatment process resulted in an enhanced digestibility and thermal degradability of biomass.
The impacts of low-transition-temperature mixtures (LTTMs) pretreatment on thermal decomposition and kinetics of empty fruit bunch (EFB) were investigated by thermogravimetric analysis. EFB was pretreated with the LTTMs under different duration of pretreatment which enabled various degrees of alteration to their structure. The TG-DTG curves showed that LTTMs pretreatment on EFB shifted the temperature and rate of decomposition to higher values. The EFB pretreated with sucrose and choline chloride-based LTTMs had attained the highest mass loss of volatile matter (78.69% and 75.71%) after 18 h of pretreatment. For monosodium glutamate-based LTTMs, the 24 h pretreated EFB had achieved the maximum mass loss (76.1%). Based on the Coats-Redfern integral method, the LTTMs pretreatment led to an increase in activation energy of the thermal decomposition of EFB from 80.00 to 82.82-94.80 kJ/mol. The activation energy was mainly affected by the demineralization and alteration in cellulose crystallinity after LTTMs pretreatment.
A promising method of Carbon dioxide (CO2) valorization is to use green microalgae photosynthesis to process biofuel. Two Phase Partitioning Bioreactors (TPPBR) offer the possibility to use non-aqueous phase liquids (NAPL) to enhance CO2 solubility; thus making CO2 available to maximize algae growth. This requires relatively less toxic hydrophobic Ionic Liquids (ILs) that comprise a new class of ionic compounds with remarkable physicochemical properties and thus qualifies them as NAPL candidates. This paper concerns the synthesis of ILs with octyl and butyl chains as well as different cations containing aromatic (imidazolium, pyridinium) and non-aromatic (piperidinum, pyrrolidinium) rings for CO2 absorption studies. The authors measured their respective toxicity levels on microalgae species, specifically, Scenedesmus quadricauda, Chlorella vulgaris and Botryococcus braunii. Results revealed that octyl-based ILs were more toxic than butyl-based analogues. Such was the case for bmim-PF6 at double saturation with an absorbance of 0.11, compared to Omim-PF6 at 0.17, bmim-NTf2 at 0.02, and Omim-NTf2 at 0.14, respectively. CO2 uptake results for ILs bearing octyl-based chains compared to the butyl analog were 54% (nCO2/nIL) (i.e., moles of CO2 moles of IL) and 38% (nCO2/nIL), respectively. Conclusively, 1-butyl-1-methylpiperidinium absorbed 13% (nCO2/nIL) and appeared the least toxic, having an absorbance of 0.25 at 688 nm (double saturation at 7 d) compared to 1-butyl-3-methylimidazolium, which showed the highest toxicity with zero absorbance. Accordingly, these findings suggest that 1-butyl-1-methylpiperidinium is capable of transporting CO2 to a system containing green microalgae without causing significant harm; thus allowing its use in TPPBR technology.
Flocculants are foreign particles that aggregate suspended microalgae cells and due to cost factor and toxicity, harvesting of microalgae biomass has shifted towards the use of bioflocculants. In this study, mild acid-extracted bioflocculants from waste chicken's eggshell and clam shell were used to harvest Chlorella vulgaris that was cultivated using chicken compost as nutrient source. It was found that a maximum of 99% flocculation efficiency can be attained at pH medium of 9.8 using 60 mg/L of hydrochloric acid-extracted chicken's eggshell bioflocculant at 50 °C of reaction temperature. On the other hand, 80 mg/L of hydrochloric acid-extracted clam shell bioflocculant was sufficient to recover C. vulgaris biomass at pH 9.8 and optimum temperature of 40 °C. The bioflocculants and bioflocs were characterized using microscopic, zeta potential, XRD, AAS and FT-IR analysis. The result revealed that calcium ions in the bioflocculants are the main contributor towards the flocculation of C. vulgaris, employing charge neutralization and sweeping as possible flocculation mechanisms. The kinetic parameters were best fitted pseudo-second order which resulted in R2 of 0.99 under optimal flocculation temperature. The results herein, disclosed the applicability of shell waste-derived bioflocculants for up-scaled microalgae harvesting for biodiesel production.
The microalgal-bacterial co-cultivation was adopted as an alternative in making microbial-based biofuel production to be more feasible in considering the economic and environmental prospects. Accordingly, the microalgal-bacterial symbiotic relationship was exploited to enhance the microbial biomass yield, while bioremediating the nitrogen-rich municipal wastewater. An optimized inoculation ratio of microalgae and activated sludge (AS:MA) was predetermined and further optimization was performed in terms of different increment ratios to enhance the bioremediation process. The nitrogen removal was found accelerating with the increase of the increment ratios of inoculated AS:MA, though all the increment ratios had recorded a near complete total nitrogen removal (94-95%). In light of treatment efficiency and lipid production, the increment ratio of 0.5 was hailed as the best microbial population size in accounting the total nitrogen removal efficiency of 94.45%, while not compromising the lipid production of 0.241 g/L. Moreover, the cultures in municipal wastewater had attained higher biomass and lipid productions of 1.42 g/L and 0.242 g/L, respectively, as compared with the synthetic wastewater which were only 1.12 g/L (biomass yield) and 0.175 g/L (lipid yield). This was possibly due to the presence of trace elements which had contributed to the increase of biomass yield; thus, higher lipid attainability from the microalgal-bacterial culture. This synergistic microalgal-bacterial approach had been proven to be effective in treating wastewater, while also producing useful biomass for eventual lipid production with comparable net energy ratio (NER) value of 0.27, obtained from the life-cycle analysis (LCA) studies. Thereby, contributing towards long-term sustainability and possible commercialization of microbial-based biofuel production.
The potential to grow attached microalgae Chlorella vulgaris in fluidized bed bioreactor was materialized in this study, targeting to ease the harvesting process prior to biodiesel production. The proposed thermodynamic mechanism and physical property assessment of various support materials verified polyurethane to be suitable material favouring the spontaneous adhesion by microalgae cells. The 1-L bioreactor packed with only 2.4% (v/v) of 1.00-mL polyurethane foam cubes could achieve the highest attached growth microalgae biomass and lipid weights of 812±122 and 376±37mg, respectively, in comparison with other cube sizes. The maturity of attached growth microalgae biomass for harvesting could also be determined from the growth trend of suspended microalgae biomass. Analysis of FAME composition revealed that the harvested microalgae biomass was dominated by C16-C18 (>60%) and mixture of saturated and mono-unsaturated fatty acids (>65%), satiating the biodiesel standard with adequate cold flow property and oxidative stability.
The conventional practice in enhancing the larvae growths is by co-digesting the low-cost organic wastes with palatable feeds for black soldier fly larvae (BSFL). In circumventing the co-digestion practice, this study focused the employment of exo-microbes in a form of bacterial consortium powder to modify coconut endosperm waste (CEW) via fermentation process in enhancing the palatability of BSFL to accumulate more larval lipid and protein. Accordingly, the optimum fermentation condition was attained by inoculating 0.5 wt% of bacterial consortium powder into CEW for 14-21 days. The peaks of BSFL biomass gained and growth rate were initially attained whilst feeding the BSFL with optimum fermented CEW. These were primarily attributed by the lowest energy loss via metabolic cost, i.e., as high as 22% of ingested optimum fermented CEW was effectively bioconverted into BSFL biomass. The harvested BSFL biomass was then found containing about 40 wt% of lipid, yielding 98% of fatty acid methyl esters of biodiesel upon transesterification. Subsequently, the protein content was also analyzed to be 0.32 mg, measured from 20 harvested BSFL with a corrected-chitin of approximately 8%. Moreover, the waste reduction index which represents the BSFL valorization potentiality was recorded at 0.31 g/day 20 BSFL. The benefit of fermenting CEW was lastly unveiled, accentuating the presence of surplus acid-producing bacteria. Thus, it was propounded the carbohydrates in CEW were rapidly hydrolysed during fermentation, releasing substantial organic acids and other nutrients to incite the BSFL assimilation into lipid for biodiesel and protein productions simultaneously.