This work aimed to study the application of liquid biphasic flotation (LBF) for the efficient and rapid recovery of astaxanthin from H. pluvialis microalgae. The performance of LBF for the extraction of astaxanthin was studied comprehensively under different operating conditions, including types and concentrations of food-grade alcohol and salt, volume ratio, addition of neutral salt, flotation period, and mass of dried H. pluvialis biomass powder. The maximum recovery, extraction efficiency and partition coefficient of astaxanthin obtained from the optimum LBF system were 95.11 ± 1.35%, 99.84 ± 0.05% and 385.16 ± 3.87, respectively. A scaled-up LBF system was also performed, demonstrating the feasibility of extracting natural astaxanthin from microalgae at a larger scale. This exploration of LBF system opens a promising avenue to the extraction of astaxanthin at lower cost and shorter processing time.
The aim of this work was to recover the cellulose fibers from EFB using low-transition-temperature-mixtures (LTTMs) as a green delignification approach. The hydrogen bonding of LTTMs observed in 1H NMR tends to disrupt the three-dimensional structure of lignin and further remove the lignin from EFB. Delignification process of EFB strands and EFB powder were performed using standard l-malic acid and cactus malic acid-LTTMs. The recovered cactus malic acid-LTTMs showed higher glucose concentration of 8.07 mg/mL than the recovered l-malic acid LTTMs (4.15 mg/mL). This implies that cactus malic acid-LTTMs had higher delignification efficiency which led to higher amount of cellulose hydrolyzed into glucose. The cactus malic acid-LTTMs-delignified EFB was the most feasible fibers for making paper due to its lowest kappa number of 69.84. The LTTMs-delignified EFB has great potential to be used for making specialty papers in pulp and paper industry.
In this present study, microalgal phycobiliproteins were isolated and purified via potential biphasic processing technique for pharmaceutical as well as food applications. The algal pre-treatment techniques were studied to enhance the yield of microalgal phycobiliproteins from the biomass. The proposed methods were optimised to obtain the best recovery yield of phycobiliproteins that can be isolated from the biomass. The phycobiliproteins were further purified using liquid biphasic system. The results showed that microalgal phycobiliproteins of high purity and yield was achieved using sonication treatment (20% power, 50% duty cycle and 7 min of irradiation time) with the biphasic system, where the purification fold of 6.17 and recovery yield of 94.89% was achieved. This work will provide insights towards the effective downstream processing of biomolecules from microalgae.
There is a growing interest in developing bio-based biodegradable plastics to reduce the dependence on depleting fossil fuels and provide a sustainable alternative. Bio-based plastics can usually be produced from lipids, proteins or carbohydrates, which are major components of microalgae. Despite its potential for algal plastics, little information is available on strain selection, culture optimization and bioplastics fabrication mechanism. In this review, we summarized the recent developments in understanding the utilization of seaweed polysaccharides, such as alginate and carrageenan for bio-based plastics. In addition, a conceptual biorefinery framework for algal plastics through promising components (e.g., lipids, carbohydrates and proteins) from microalgae is comprehensively presented. Moreover, the reasons for variations in bioplastics performance and underlying mechanism of various algal biocomposites have been critically discussed. We believe this review can provide valuable information to accelerate the development of innovative green technologies for improving the commercial viability of algal plastics.
In the present study, catalytic pyrolysis of Chlorella vulgaris biomass was conducted to analyse the kinetic and thermodynamic performances through thermogravimetric approach. HZSM-5 zeolite, limestone (LS), bifunctional HZSM-5/LS were used as catalysts and the experiments were heated from 50 to 900 °C at heating rates of 10-100 °C/min. Iso-conversional model-free methods such as Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), Starink's, and Vyazovkin (V) were employed to evaluate the kinetic parameters meanwhile the thermodynamic parameters were determined by using FWO and KAS methods. The calculated EA values of non-catalytic and catalytic pyrolysis of HZSM-5 zeolite, LS, and bifunctional HZSM-5/LS were determined to be in the range of 156.16-158.10 kJ/mol, 145.26-147.84 kJ/mol, 138.81-142.06 kJ/mol, and 133.26 kJ/mol respectively. The results have shown that catalytic pyrolysis with the presence of bifunctional HZSM-5/LS resulted to a lower average EA and ΔH compared to HZSM-5, and LS which indicated less energy requirement in the process.
Polyhydroxyalkanoates (PHAs), a family of biodegradable and renewable biopolymers show a huge potential as an alternative to conventional plastics. Extractive bioconversion (in situ product recovery) is a technique that integrates upstream fermentation and downstream purification. In this study, extractive bioconversion of PHAs from Cupriavidus necator H16 was performed via a thermo-separating aqueous two-phase system to reduce the cost and environmental impacts of PHAs production. Key operating parameters, such as polymer concentration, temperature, and pH, were optimized. The strategy achieved a yield and PF of 97.6% and 1.36-fold, respectively at 5% EOPO 3900 concentration, 30 °C fermentation temperature and pH 6. The PHAs production process was also successfully scaled up in a 2 L bioreactor. To the best of our knowledge, this is the first report on extractive fermentation of PHAs from Cupriavidus necator utilizing a thermo-separation system to achieve a better productivity and purity of the target product.
Liquid biphasic flotation (LBF), an integrated process of liquid biphasic system (LBS) and adsorptive bubbles flotation, was used for the purification of C-phycocyanin from S. platensis microalgae. Various experimental parameters such as type of phase forming polymer and salt, concentration of phase forming components, system pH, volume ratio, air flotation time and crude extract concentration were evaluated to maximise the C-phycocyanin recovery yield and purity. The optimal conditions for the LBF system achieving C-phycocyanin purification fold of 3.49 compared to 2.43 from the initial LBF conditions was in polyethylene glycol (PEG) 4000 and potassium phosphate combination, with 250 g/L of polymer and salt concentration each, volume ratio of 1:0.85, system pH of 7.0, air flotation duration of 7 min and phycocyanin crude extract concentration of 0.625 %w/w. The LBF has effectively enhanced the purification of C-phycocyanin in a cost effective and simple processing.
Haematococcus pluvialis is one of the most abundant sources of natural astaxanthin as compared to others microorganism. Therefore, it is important to understand the biorefinery of astaxanthin from H. pluvialis, starting from the cultivation stage to the downstream processing of astaxanthin. The present review begins with an introduction of cellular morphologies and life cycle of H. pluvialis from green vegetative motile stage to red non-motile haematocyst stage. Subsequently, the conventional biorefinery methods (e.g., mechanical disruption, solvent extraction, direct extraction using vegetable oils, and enhanced solvent extraction) and recent advanced biorefinery techniques (e.g., supercritical CO2 extraction, magnetic-assisted extraction, ionic liquids extraction, and supramolecular solvent extraction) were presented and evaluated. Moreover, future prospect and challenges were highlighted to provide a useful guide for future development of biorefinery of astaxanthin from H. pluvialis. The review aims to serve as a present knowledge for researchers dealing with the bioproduction of astaxanthin from H. pluvialis.
An advanced electrodialysis fermentation system was set up to remove ammonium during hydrogen fermentation. When the voltage was increased from 0 to 6 V, the average ammonium removal rate was improved from 8.7 to 31.1 mg/L/h at an initial ammonium concentration of 3000 mg/L. A model based on the Nernst-Plank equation and porous media properties of ion exchange membranes was successfully implemented to predict the ammonium removal performance. When such a system was fed with synthetic wastewater at an ammonium concentration of 3000 mg/L for hydrogen fermentation, a significant increase in specific hydrogen yield was observed in the experiment group at 4 V. Specific hydrogen yield was 225.0 mL/g glucose, this value is 47.9% higher than the control. Moreover, ammonium concentration in experiment group was reduced to 701.6 mg/L at 72 h when voltage was set at 4 V, which is 63.7% lower than that in 0 V experiment group.
Third generation biofuels, also known as microalgal biofuels, are promising alternatives to fossil fuels. One attractive option is microalgal biodiesel as a replacement for diesel fuel. Chlamydomonas sp. Tai-03 was previously optimized for maximal lipid production for biodiesel generation, achieving biomass growth and productivity of 3.48 ± 0.04 g/L and 0.43 ± 0.01 g/L/d, with lipid content and productivity of 28.6 ± 1.41% and 124.1 ± 7.57 mg/L/d. In this study, further optimization using 5% CO2 concentration and semi-batch operation with 25% medium replacement ratio, enhanced the biomass growth and productivity to 4.15 ± 0.12 g/L and 1.23 ± 0.02 g/L/d, with lipid content and productivity of 19.4 ± 2.0% and 239.6 ± 24.8 mg/L/d. The major fatty acid methyl esters (FAMEs) were palmitic acid (C16:0), oleic acid (C18:1), and linoleic acid (C18:2). These short-chain FAMEs combined with high growth make Chlamydomonas sp. Tai-03 a suitable candidate for biodiesel synthesis.
To valorize biomass waste, pyrolysis of orange peel was mainly investigated as a case study. In an effort to establish a more sustainable thermolytic platform for orange peel, this study particularly employed CO2 as reactive gas medium. Accordingly, this study laid great emphasis on elucidating the mechanistic role of CO2 in pyrolysis of orange peel. The thermo-gravimetric analysis (TGA) confirmed that no occurrence of the heterogeneous reactions between the solid sample and CO2. However, the gaseous effluents from pyrolysis of orange peel experimentally proved that CO2 effectively suppressed dehydrogenation of volatile matters (VMs) evolved from the thermolysis of orange peel by random bond scissions. Moreover, CO2 reacted VMs, thereby resulting in the formation of CO. Note that the formation of CO was being initiated at temperatures ≥550 °C. The two identified roles of CO2 led to the compositional modification of pyrolytic oil by means of lowering aromaticity.
In this study, acidic deep eutectic solvents (DES) synthesized from various organic carboxylic acid hydrogen bond donors were applied to lignocellulosic oil palm empty fruit bunch (EFB) pretreatment. The influence of functional group types on acid and their molar ratios with hydrogen bond acceptor on lignin extraction were evaluated. The result showed presence of hydroxyl group and short alkyl chain enhanced biomass fractionation and lignin extraction. Choline chloride:lactic acid (CC-LA) with the ratio of 1:15 and choline chloride:formic acid (CC-FA) with 1:2 ratio extracted more than 60 wt% of lignin. CC-LA DES-extracted lignin (DEEL) exhibited comparable reactivity with technical and commercial lignin based on its phenolic hydroxyl content (3.33-3.72 mmol/glignin). Also, the DES-pretreated EFB comprised of enriched glucan content after biopolymer fractionation. Both DES-pretreated EFB and DEEL can be potential feedstock for subsequent conversion processes. This study presented DES as an effective and facile pretreatment method for reactive lignin extraction.
In this work, a novel solvent, deep eutectic solvent (DES) was applied to examine its effectiveness in pretreating OPEFB. Three types of DESs, i.e. choline chloride-lactic acid (ChCl-LA), choline chloride-urea (ChCl-U) and choline chloride-glycerol (ChCl-G) were investigated. The pretreatment performance was based on cellulose digestibility, structural and morphology changes. At molar ratio of 1:2, ChCl-LA attained the highest reducing sugars yield of 20.7%, followed by ChCl-G (20.0%) and ChCl-U (16.9%). FT-IR and SEM results further confirmed the outstanding ability of ChCl-LA due of its ability in cellulose, hemicellulose and lignin disruption, exposing its cellulose fraction to enzymatic hydrolysis. ChCl-LA is also more favorable compare to acid and alkaline solvents as it could prevent sugars loss, use of expensive corrosion resistant equipment and ease products separation.
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.
Previous studies on screening of lignin-degrading bacteria mainly focused on the ligninolytic ability of the isolated bacteria for the utilization of lignin monomers. In this study, we focused on the depolymerization of alkali lignin to prove the ability of the isolated thermophilic bacterial strains to utilize and depolymerize more than a monomer of alkali lignin within 7 days of incubation. Indigenous thermophilic bacterial isolates from the palm oil plantation were used to evaluate the depolymerization and utilization of alkali lignin. The confirmation of the bacterium-mediated depolymerization of oil palm empty fruit bunch was achieved through the removal of silica bodies, as observed with scanning electron microscopy. Stenotrophomonas sp. S2 and Bacillus subtilis S11Y were able to reduce approximately 50% and 20% of alkali lignin at 7 days of incubation without the requirement for additional carbon sources.
This study aimed to investigate the transport mechanisms of ions during forward-osmosis-driven (FO-driven) dewatering of microalgae using molecular dynamics (MD) simulations. The dynamical and structural properties of ions in FO systems of varying NaCl or MgCl2 draw solution (DS) concentrations were calculated and correlated. Results indicate that FO systems with higher DS concentration caused ions to have lower hydration numbers and higher coordination numbers leading to lower diffusion coefficients. The higher hydration number of Mg2+ ions resulted in significantly lower ionic permeability as compared to Na+ ions at all concentrations (p = 0.002). The simulations also revealed that higher DS concentrations led to higher accumulation of ions in the membrane. This study provides insights on the proper selection of DS for FO systems.
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.
The performances of various anhydrous and aqueous choline chloride-dicarboxylic acid based deep eutectic solvents (DESs) were evaluated for furfural production from oil palm fronds without any additional catalyst. The effects of different carbon chain length dicarboxylic acids and water content in each DES on furfural production were investigated. Oil palm fronds, DES and water (0-5 ml) were mixed and reacted in an oil bath (60-300 min). Reacted oil palm fronds had the potential to be reused as cellulose-rich-valuable by-products. At 100 °C, aqueous choline chloride-oxalic acid (16.4 wt% H2O) produced the highest furfural yield of 26.34% and cellulose composition up to 72.79% in the reacted oil palm fronds. Despite operating at suitable reaction duration for dicarboxylic acid with longer carbon chain length, aqueous choline chloride-malonic acid and aqueous choline chloride-succinic acid performed poorly with furfural yield of less than 1%.
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 aim of this study was to pyrolyze individual (oil palm shell, empty fruit bunch and sawdust) as well as blend biomass in a thermogravimetric mass spectrometry (TG-MS) from room temperature to 800 °C at constant heating rate of 15 °C/min. The results showed that the onset TG temperature for blend biomass shifted slightly to lower values. Activation energy values were also found to decrease slightly after blending the biomass. Interestingly, the MS spectra of selected gases (H2O CH4, H2O, C2H2, C2H4 or CO, CH2O, CH3OH, HCl, C3H6, CO2, HCOOH, and C6H12) evolved from blend biomass showed decreased in the intensity as compared to their individual biomass. Overall, the blend biomass showed synergy which provides ways to expand the possibility of utilizing multiple feedstocks in one thermo-chemical system.