Techno-economic assessment of hydrotreated vegetable oil as a renewable fuel from waste sludge palm oil.

To date, the development of renewable fuels has become a normal phenomenon to solve the problem of diesel fuel emissions and the scarcity of fossil fuels. Biodiesel production has some limitations, such as two-step processes requiring high free fatty acids (FFAs), oil feedstocks and gum formation. Hydrotreated vegetable oil (HVO) is a newly developed international renewable diesel that uses renewable feedstocks via the hydrotreatment process. Unlike FAME, FFAs percentage doesn't affect the HVO production and sustains a higher yield. The improved characteristics of HVO, such as a higher cetane value, better cold flow properties, lower emissions and excellent oxidation stability for storage, stand out from FAME biodiesel. Moreover, HVO is a hydrocarbon without oxygen content, but FAME is an ester with 11% oxygen content which makes it differ in oxidation stability. Waste sludge palm oil (SPO), an abundant non-edible industrial waste, was reused and selected as the feedstock for HVO production. Techno-economical and energy analyses were conducted for HVO production using Aspen HYSYS with a plant capacity of 25,000 kg/h. Alternatively, hydrogen has been recycled to reduce the hydrogen feed. With a capital investment of RM 65.86 million and an annual production cost of RM 332.56 million, the base case of the SPO-HVO production process was more desirable after consideration of all economic indicators and HVO purity. The base case of SPO-HVO production could achieve a return on investment (ROI) of 89.03% with a payback period (PBP) of 1.68 years. The SPO-HVO production in this study has observed a reduction in the primary greenhouse gas, carbon dioxide (CO2) emission by up to 90% and the total annual production cost by nearly RM 450 million. Therefore, SPO-HVO production is a potential and alternative process to produce biobased diesel fuels with waste oil.

Advancement of biorefinery-derived platform chemicals from macroalgae: a perspective for bioethanol and lactic acid.

The extensive growth of energy and plastic demand has raised concerns over the depletion of fossil fuels. Moreover, the environmental conundrums worldwide integrated with global warming and improper plastic waste management have led to the development of sustainable and environmentally friendly biofuel (bioethanol) and biopolymer (lactic acid, LA) derived from biomass for fossil fuels replacement and biodegradable plastic production, respectively. However, the high production cost of bioethanol and LA had limited its industrial-scale production. This paper has comprehensively reviewed the potential and development of third-generation feedstock for bioethanol and LA production, including significant technological barriers to be overcome for potential commercialization purposes. Then, an insight into the state-of-the-art hydrolysis and fermentation technologies using macroalgae as feedstock is also deliberated in detail. Lastly, the sustainability aspect and perspective of macroalgae biomass are evaluated economically and environmentally using a developed cascading system associated with techno-economic analysis and life cycle assessment, which represent the highlights of this review paper. Furthermore, this review provides a conceivable picture of macroalgae-based bioethanol and lactic acid biorefinery and future research directions that can be served as an important guideline for scientists, policymakers, and industrial players.

Facile asymmetric modification of graphene nanosheets using κ-carrageenan as a green template.

The synthesis of Janus nanosheets using κ-carrageenan (κ-Ca) as a green template endows a greener and more straightforward method compared to traditional approaches of using wax template. We hypothesize that the hydrogen bonding interaction between κ-Ca and graphene oxide (GO) allows partial masking of GO's single facet, paving the way for the asymmetric modification of the exposed surface. GO is first encapsulated within the porous hydrogel matrix formed by κ-Ca to isolate one of the facets. The exposed surface was then selectively hydrophobized to produce an amphiphilic asymmetrically modified graphene oxide (AMGO). The properties of AMGO synthesized under different κ-Ca/GO ratios were studied. The κ-Ca/GO interactions and the properties of GO and AMGO were investigated and characterized. AMGO was successfully produced with a yield of 90.37 % under optimized synthesis conditions. The separation of κ-Ca and AMGO was conducted without organic solvents, and the κ-Ca could be subsequently recovered. Furthermore, the porous hydrogel matrix formed by κ-Ca and GO exhibited excellent shape-retaining properties with high thermal tolerance of up to 50 °C. Given these benefits, this newly developed method endows sustainability and open the possibility of formulating more flexible material synthesis protocols.

Anaerobic digestate as a low-cost nutrient source for sustainable microalgae cultivation: A way forward through waste valorization approach.

To suffice the escalating global energy demand, microalgae are deemed as high potential surrogate feedstocks for liquid fuels. The major encumbrance for the commercialization of microalgae cultivation is due to the high costs of nutrients such as carbon, phosphorous, and nitrogen. Meanwhile, the organic-rich anaerobic digestate which is difficult to be purified by conventional techniques is appropriate to be used as a low-cost nutrient source for the economic viability and sustainability of microalgae production. This option is also beneficial in terms of reutilize the organic fraction of solid waste instead of discarded as zero-value waste. Anaerobic digestate is the side product of biogas production during anaerobic digestion process, where optimum nutrients are needed to satisfy the physiological needs to grow microalgae. Besides, the turbidity, competing biological contaminants, ammonia and metal toxicity of the digestate are also potentially contributing to the inhibition of microalgae growth. Thus, this review is aimed to explicate the feasibility of utilizing the anaerobic digestate to cultivate microalgae by evaluating their potential challenges and solutions. The proposed potential solutions (digestate dilution and pre-treatment, microalgae strain selection, extra organics addition, nitrification and desulfurization) corresponding to the state-of-the-art challenges are applicable as future directions of the research.

Sustainable and green pretreatment strategy of Eucheuma denticulatum residues for third-generation l-lactic acid production.

Managing plastic waste remains an urgent environmental concern and switching to biodegradable plastics can reduce the dependence on depleting fossil fuels. This study emphasises the efficacy of macroalgae wastes, Eucheuma denticulatum residues (EDRs), as potential alternate feedstock to produce l-lactic acid (l-LA), the monomer of polylactic acid, through fermentation. An innovative environmental friendly strategy was explored in this study to develop a glucose platform from EDRs: pretreatment with microwave-assisted autohydrolysis (MAA) applied to enhance enzymatic hydrolysis of EDRs. The results indicate that MAA pretreatment significantly increased the digestibility of EDRs during the enzymatic hydrolysis process. The optimum pretreatment conditions were 120 °C and 50 min, resulting in 96.5% of enzymatic digestibility after 48 h. The high l-LA yield of 98.6% was obtained using pretreated EDRs and supplemented with yeast extract. The energy analysis implies that MAA pretreatment could further improve the overall energy efficiency of the process.

Third-generation L-Lactic acid production by the microwave-assisted hydrolysis of red macroalgae Eucheuma denticulatum extract.

The development of an efficient third-generation L-lactic acid (L-LA) production process from Eucheuma denticulatum extract (EDE) was achieved in this study. Microwave-assisted dilute acid hydrolysis (MADAH) and microwave-assisted hydrothermal hydrolysis (MAHTH) were chosen as the hydrolysis of EDE for the objective of increasing galactose yield. Single-factor optimization of hydrolysis of the EDE was studied, MADAH had high performance in galactose production relative to MAHTH, in which the yield and optimal conditions for both processes were 50.7% (0.1 M H2SO4, 120 °C for 25 min) and 47.8% (0 M H2SO4,160 °C for 35 min), respectively. For fermentation, the optimal L-LA yield was achieved at the inoculum cell density of 4% (w/w) Bacillus coagulans ATCC 7050 with 89.4% and 6% (w/w) Lactobacillus acidophilus LA-14 with 87.6%. In addition, lipid-extracted Chlorella vulgaris residues (CVRs) as co-nutrient supplementation increased the relative abundance of B. coagulans ATCC 7050, thus benefiting L-LA production.

Macroalgae-derived regenerated cellulose in the stabilization of oil-in-water Pickering emulsions.

This study aims to derive regenerated cellulose (RC) from lignin/hemicellulose-free Eucheuma cottonii for its independent stabilization of Pickering emulsion. The RC exhibits a fibrillar morphology with diameters ranging from 17 to 157 nm and stabilizes paraffin oil-Pickering emulsions without any co-stabilizer. It was found that the emulsion stability, viscosities and viscoelasticity correlate positively with RC concentration. All emulsion samples depict gel-like behavior. Under different oil fraction at a constant RC concentration, anomalies were found in emulsion properties. This can be attributed to the aggregating behavior of RC at the oil-water interface, the degree of gel-like structure formation due to materials interaction within the emulsion system, and the variations of microscopic droplet cluster interactions under shear condition. The emulsions portrayed excellent robustness against harsh salinity, high temperature and extreme pH fluctuation. Hence, these findings had elucidated the plausibility of macroalgae-derived RC in enhanced oil recovery application.

Dilute sulfuric acid hydrolysis of red macroalgae Eucheuma denticulatum with microwave-assisted heating for biochar production and sugar recovery.

This study aims to produce biochar and sugars from a macroalga Eucheuma denticulatum using dilute sulfuric acid hydrolysis along with microwave-assisted heating. The reactions were operated at sulfuric acid concentrations of 0.1 and 0.2M, reaction temperatures of 150-170°C and a heating time of 10min. Compared to the raw macroalga, biochar qualities were improved with increased carbon content and lower ash and moisture contents. The calorific value of the biochar could be intensified up to 45%, and 39% of energy yield was recovered. Apart from producing biochar, the highest total reducing sugars were 51.47g/L (74.84% yield) along with a low by-product 5-HMF of 0.20g/L, when the biomass was treated under the optimum conditions at 160°C with 0.1M H2SO4. Thus, this study demonstrated that macroalgae could be potentially used as biomass feedstock under microwave-assisted acid hydrolysis for the production of biofuel and value-added products.

Comparison of different process strategies for bioethanol production from Eucheuma cottonii: An economic study.

The aim of this work was to evaluate the efficacy of red macroalgae Eucheuma cottonii (EC) as feedstock for third-generation bioethanol production. Dowex (TM) Dr-G8 was explored as a potential solid catalyst to hydrolyzed carbohydrates from EC or macroalgae extract (ME) and pretreatment of macroalgae cellulosic residue (MCR), to fermentable sugars prior to fermentation process. The highest total sugars were produced at 98.7 g/L when 16% of the ME was treated under the optimum conditions of solid acid hydrolysis (8% (w/v) Dowex (TM) Dr-G8, 120°C, 1h) and 2% pretreated MCR (P-MCR) treated by enzymatic hydrolysis (pH 4.8, 50°C, 30 h). A two-stream process resulted in 11.6g/L of bioethanol from the fermentation of ME hydrolysates and 11.7 g/L from prehydrolysis and simultaneous saccharification and fermentation of P-MCR. The fixed price of bioethanol obtained from the EC is competitive with that obtained from other feedstocks.

Solid acid catalysts pretreatment and enzymatic hydrolysis of macroalgae cellulosic residue for the production of bioethanol.

The aim of this study is to investigate the technical feasibility of converting macroalgae cellulosic residue (MCR) into bioethanol. An attempt was made to present a novel, environmental friendly and economical pretreatment process that enhances enzymatic conversion of MCR to sugars using Dowex (TM) Dr-G8 as catalyst. The optimum yield of glucose reached 99.8% under the optimal condition for solid acid pretreatment (10%, w/v biomass loading, 4%, w/v catalyst loading, 30min, 120°C) followed by enzymatic hydrolysis (45FPU/g of cellulase, 52CBU/g of ß-glucosidase, 50°C, pH 4.8, 30h). The yield of sugar obtained was found more superior than conventional pretreatment process using H2SO4 and NaOH. Biomass loading for the subsequent simultaneous saccharification and fermentation (SSF) of the pretreated MCR was then optimized, giving an optimum bioethanol yield of 81.5%. The catalyst was separated and reused for six times, with only a slight drop in glucose yield.

Immobilization of ß-glucosidase from Aspergillus niger on κ-carrageenan hybrid matrix and its application on the production of reducing sugar from macroalgae cellulosic residue.

A novel concept for the synthesis of a stable polymer hybrid matrix bead was developed in this study. The beads were further applied for enzyme immobilization to produce stable and active biocatalysts with low enzyme leakage, and high immobilization efficiency, enzyme activity, and recyclability. The immobilization conditions, including PEI concentration, activation time and pH of the PEI solution were investigated and optimized. All formulated beads were characterized for its functionalized groups, composition, surface morphology and thermal stability. Compared with the free ß-glucosidase, the immobilized ß-glucosidase on the hybrid matrix bead was able to tolerate broader range of pH values and higher reaction temperature up to 60 °C. The immobilized ß-glucosidase was then used to hydrolyse pretreated macroalgae cellulosic residue (MCR) for the production of reducing sugar and a hydrolysis yield of 73.4% was obtained. After repeated twelve runs, immobilized ß-glucosidase retained about 75% of its initial activity.

Hydrolysis of macroalgae using heterogeneous catalyst for bioethanol production.

Utilization of macroalgae biomass for bioethanol production appears as an alternative source to lignocellulosic materials. In this study, for the first time, Amberlyst (TM)-15 was explored as a potential catalyst to hydrolyze carbohydrates from Eucheuma cottonii extract to simple reducing sugar prior to fermentation process. Several important hydrolysis parameters were studied for process optimization including catalyst loading (2-5%, w/v), reaction temperature (110-130°C), reaction time (0-2.5 h) and biomass loading (5.5-15.5%, w/v). Optimum sugar yield of 39.7% was attained based on the following optimum conditions: reaction temperature at 120°C, catalyst loading of 4% (w/v), 12.5% (w/v) of biomass concentration and reaction time of 1.5h. Fermentation of the hydrolysate using Saccharomyces cerevisiae produced 0.33 g/g of bioethanol yield with an efficiency of 65%. The strategy of combining heterogeneous-catalyzed hydrolysis and fermentation with S. cerevisiae could be a feasible strategy to produce bioethanol from macroalgae biomass.