Modelling photoperiod in enhancing hydrogen production from Chlorella vulgaris sp. while bioremediating ammonium and organic pollutants in municipal wastewater.

Municipal wastewater is ubiquitously laden with myriad pollutants discharged primarily from a combination of domestic and industrial activities. These heterogeneous pollutants are threating the natural environments when the traditional activated sludge system fails sporadically to reduce the pollutants' toxicities. Besides, the activated sludge system is very energy intensive, bringing conundrums for decarbonization. This research endeavoured to employ Chlorella vulgaris sp. In converting pollutants from municipal wastewater into hydrogen via alternate light and dark fermentative process. The microalgae in attached form onto 1 cm3 of polyurethane foam cubes were adopted in optimizing light intensity and photoperiod during the light exposure duration. The highest hydrogen production was recorded at 52 mL amidst the synergistic light intensity and photoperiod of 200 µmolm-2s-1 and 12:12 h (light:dark h), respectively. At this lighting condition, the removals of chemical oxygen demand (COD) and ammoniacal nitrogen were both achieved at about 80%. The sustainability of microalgal fermentative performances was verified in recyclability study using similar immobilization support material. There were negligible diminishments of hydrogen production as well as both COD and ammoniacal nitrogen removals after five cycles, heralding inconsequential microalgal cells' washout from the polyurethane support when replacing the municipal wastewater medium at each cycle. The collected dataset was finally modelled into enhanced Monod equation aided by Python software tool of machine learning. The derived model was capable to predict the performances of microalgae to execute the fermentative process in producing hydrogen while subsisting municipal wastewater at arbitrary photoperiod. The enhanced model had a best fitting of R2 of 0.9857 as validated using an independent dataset. Concisely, the outcomes had contributed towards the advancement of municipal wastewater treatment via microalgal fermentative process in producing green hydrogen as a clean energy source to decarbonize the wastewater treatment facilities.

Direct Oxidation of Hibiscus cannabinus Stalks to Vanillin Using CeO2 Nanostructure Catalysts.

Biomass lignin can be used to produce vanillin through an oxidation process. Although its purity is high, the processing time and separation efficiency are not ideal. This research aims to produce vanillin directly from Kenaf stalks without separating the lignin first from the lignocellulosic biomass. This method is greener because it does not require the separation of cellulose and hemicellulose from the biomass, thus minimizing the use of acid and alkaline solutions and saving time. A high oxygen storage capacity and release capacity of ceria as an oxidation catalyst contribute to the reversable redox properties between Ce4+ and Ce3+ in ceria lattice. Cerium oxide nanostructures were synthesized using a hydrothermal method treated under alkaline NaOH, followed by drying at 120 °C for 16 h and calcining at different temperatures between 400 and 600 °C for the direct oxidation of Kenaf stalks to vanillin under microwave irradiation. The catalysts were characterized for their physicochemical properties using XRD, N2 adsorption-desorption isotherms and TEM. All synthesized CeO2 nanostructures showed the presence of diffraction peaks assigned to the presence of cubic fluorite. The N2 adsorption-desorption isotherms showed that all catalysts possess a Type IV isotherm, indicating a mesoporous structure. The TEM image shows the uniform shape of the CeO2 nanostructures, while HRTEM images show that the CeO2 nanostructures are single-crystalline in nature. All catalysts were tested for the direct oxidation of Kenaf stalks using H2O2 as the oxidizing agent in temperatures ranging from 160 to 180 °C for 10-30 min with 0.1-0.3 g catalyst loading under 100-500 W of microwave irradiation. The CeO2-Nps-400 catalyst produced the highest vanillin yields of 3.84% and 4.32% for the direct oxidation of Kenaf stalks and extraction of lignin from Kenaf stalks, respectively. Compared to our earlier study, the highest vanillin yields of 2.90% and 3.70% for direct biomass and extracted lignin were achieved using a Ce/MgO catalyst.

Levulinic Acid Production from Waste Corncob Biomass Using an Environmentally Benign WO3-Grafted ZnCo2O4@CeO2 Bifunctional Heterogeneous Catalyst.

Herein, a novel and environmentally benign solid catalyst was fabricated by grafting WO3 active species onto the ZnCo2O4@CeO2 support for efficient levulinic acid production from corncob waste biomass. The morphological, compositional, and textural properties of the designed catalyst were investigated using different characterization techniques to identify suitable catalyst formulation with enhanced catalytic activity and stability. The results demonstrated that WO3 active species were successfully loaded with uniform distribution onto the support to develop a robust catalyst with both acidic and basic sites. The experimental investigation showed that among the catalysts, WO3(10 wt %)/ZnCo2O4@CeO2 exhibited the best catalytic activity, providing a maximum levulinic acid yield of 78.49% at the optimal conditions of 6 wt % catalyst dosage, reaction temperature of 180 °C, and reaction time of 200 min. The presence of an optimum number of both acid and base active sites on the catalyst surface could lead to the highest catalytic activity of the synthesized catalyst. Finally, the reusability investigation indicated that the synthesized catalyst possessed sufficient recyclability of up to four times for the levulinic acid production from the selected biomass with negligible drop in the catalytic activity.

Ce-Zr-based mixed oxide catalyst for oxidative depolymerization of kenaf stalk (biomass) into vanillin.

Since petroleum became depleted, rapid attention has been devoted to renewable energy sources such as lignocellulosic biomass to produce useful chemicals for industry (for instance vanillin). Three primary components of lignocellulose are lignin, cellulose, and hemicellulose. This paper uses microwave-assisted technology to oxidize the kenaf stalk (lignocellulosic biomass) and extract lignin to produce vanillin. Catalysts with variable acid-base and redox properties are essential for the mentioned effective conversion, for this reason, CeO2-CA, ZrO2-CA, and CeZrO2-CA catalysts were synthesized. The citrate complexation method was used for the catalyst synthesis and the physicochemical characteristics were analyzed by XRD, FTIR, FE-SEM, TEM, BET, and TPO. The characterization results demonstrated that CeZrO2-CA shows the smallest sized crystallites with a large specific surface area among the other chosen catalysts. For vanillin production, the effect of reaction temperature, reaction time, and catalyst loading was studied. It was observed that compared to other catalysts, CeZrO2-CA produced the highest vanillin yield of 9.90% for kenaf stalk for 5 wt% of CeZrO2-CA at 160 °C for 30 min. Furthermore, vanillin production using extracted lignin is studied keeping CeZrO2-CA as a catalyst and with the same operating parameters, which yielded 14.3% of vanillin. Afterward, the change in yield with respect to pH is also presented. Finally, the recyclability of catalyst is also studied, which showed that it has a strong metal support and greater stability which may give industrial applications a significant boost.

Correlating black soldier fly larvae growths with soluble nutrients derived from thermally pre-treated waste activated sludge.

Black soldier fly larvae (BSFL) have been deployed to valorize various organic wastes. Nonetheless, its growth rate whilst being offered with waste activated sludge (WAS) is not promising, likely by virtue of the presence of extracellular polymeric substances' structure in WAS. In this work, the WAS were first thermally pre-treated under different treatment temperatures and durations before being administered as the feeding substrates for BSFL. The results showed the thermal pre-treatment could improve WAS palatability and subsequently, enhance the growth of BSFL especially after the pre-treatments at 75 °C and above. The highest larva weight gained was recorded at 2.16 mg/larva for the WAS sample being pre-treated at 90 °C and 16 h. Furthermore, the samples pre-treated above 75 °C also achieved higher degradation rates, indicating that the 75 °C was a threshold temperature to effectively hydrolyze the WAS. The changes of WAS characteristics, namely, (i) soluble chemical oxygen demand (SCOD), (ii) soluble carbohydrate, (iii) soluble protein, (iv) humic substances and (v) total soluble protein and humic substances, after the thermal pre-treatments were also studied in correlating with the BSFL growth. Accordingly, a model was successfully developed with the highest R2 value attained at 0.95, evidencing the SCOD was the most suitable WAS characteristic to accurately predict the BSFL growth behavior.

Physio-Chemical Analysis of Amide and Amine Poly(dimethylsiloxane)-Modified Defoamer for Efficient Oil-Water Separation.

The formation of foam due to the injection of surfactant foam in FAWAG causes significant problems in the oil well production and separation facilities. The excessive foam can lead to the reduction of the separator capacity as well as its efficiency. A defoamer is needed to break and destroy the foam in the separator. There are many commercially available defoamer agents in the market, but not all defoamers are suitable for every application. For this reason, four modified silicone-based defoamers were successfully synthesized and characterized based on the data obtained from the screening process using various commercial defoamers. The performance of modified defoamers was evaluated using TECLIS FoamScan that imitate real conditions of treatment. The results show that all four of the modified silicone-based defoamers, especially amide-terminated-modified defoamers (S2) showed excellent performance as a defoaming agent to mitigate foam in specific conditions. The best-case condition for the modified defoamer to perform was at a high temperature (60 °C), gas flow rate of 1.0 L/min, and low ration concentration of the surfactant to brine (30:70). The study on the bubble count and distribution using a KRÜSS Dynamic Foam Analyzer revealed that S2 excellently contributes to the formation of unstable foam that can fasten foam destruction in the foaming system.

A Critical Review on Metal-Organic Frameworks and Their Composites as Advanced Materials for Adsorption and Photocatalytic Degradation of Emerging Organic Pollutants from Wastewater.

Water-borne emerging pollutants are among the greatest concern of our modern society. Many of these pollutants are categorized as endocrine disruptors due to their environmental toxicities. They are harmful to humans, aquatic animals, and plants, to the larger extent, destroying the ecosystem. Thus, effective environmental remediations of these pollutants became necessary. Among the various remediation techniques, adsorption and photocatalytic degradation have been single out as the most promising. This review is devoted to the compilations and analysis of the role of metal-organic frameworks (MOFs) and their composites as potential materials for such applications. Emerging organic pollutants, like dyes, herbicides, pesticides, pharmaceutical products, phenols, polycyclic aromatic hydrocarbons, and perfluorinated alkyl substances, have been extensively studied. Important parameters that affect these processes, such as surface area, bandgap, percentage removal, equilibrium time, adsorption capacity, and recyclability, are documented. Finally, we paint the current scenario and challenges that need to be addressed for MOFs and their composites to be exploited for commercial applications.

Tailoring the surface area and the acid-base properties of ZrO2 for biodiesel production from Nannochloropsis sp.

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.

Catalytic hydrodeoxygenation of rubber seed oil over sonochemically synthesized Ni-Mo/γ-Al2O3 catalyst for green diesel production.

Hydrodeoxygenation is one of the promising technologies for the transformation of triglycerides into long-chain hydrocarbon fuel commonly known as green diesel. The hydrodeoxygenation (HDO) of rubber seed oil into diesel range (C15-C18) hydrocarbon over non-sulphided bimetallic (Ni-Mo/γ-Al2O3 solid catalysts were studied. The catalysts were synthesized via wet impregnation method as well as sonochemical method. The synthesized catalysts were subjected to characterization methods including FESEM coupled with EDX, XRD, BET, TEM, XPS, NH3-TPD, CO-chemisorption and H2-TPR in order to investigate the effects of ultrasound irradiations on physicochemical properties of the catalyst. All the catalysts were tested for HDO reaction at 350 °C, 35 bar, H2/oil 1000 N (cm3/cm3) and WHSV = 1 h-1 in fixed bed tubular reactor. The catalyst prepared via sonochemical method showed comparatively higher specific surface area, particles in nano-size and uniform distribution of particle on the external surface of the support, higher crystallinity and lower reduction temperature as well as higher concentration of Mo4+ deoxygenating metal species. These physicochemical properties improved the catalytic activity compared to conventionally synthesized catalyst for HDO of rubber seed oil. The catalytic performance of sonochemically synthesized Ni-Mo/γ-Al2O3 catalyst (80.87%) was higher than the catalyst prepared via wet impregnation method (63.3%). The sonochemically synthesized Ni-Mo/γ-Al2O3 catalyst is found to be active, produces 80.87 wt% of diesel range hydrocarbons, and it gives high selectivity for Pentadecane (18.7 wt%), Hexadecane (16.65 wt%), Heptadecane (24.45 wt%) and Octadecane (21.0 wt%). The product distribution revealed that the deoxygenation reaction pathway was preferred. Higher conversion and higher HDO yield in this study are associated mainly with the change in concentration ratio between oxidation states of molybdenum (Mo4+, Mo5+, and Mo6+) on the external surface of the catalyst due to ultrasound irradiation during the synthesis process. Consequently, the application of sonochemically synthesized non-sulphided catalysts favored mainly hydrodeoxygenation of diesel range hydrocarbon.

A Kinetic Approach of DPPH Free Radical Assay of Ferulate-Based Protic Ionic Liquids (PILs).

The antiradical efficiency (AE) and kinetic behavior of a new ferulate-based protic ionic liquids (PILs) were described using 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical assay. The reduction of the DPPH free radical (DPPH•) was investigated by measuring the decrease in absorbance at 517 nm. The time to reach steady state for the reaction of parent acid (ferulic acid) and synthesized PILs with DPPH• was continuously recorded for 1 h. Results revealed that the AE of 2-butylaminoethanol ferulate (2BAEF), 3-dimethylaminopropanol ferulate (3DMAPF) and 3-diethylaminopropanol ferulate (3DEAPF) PILs have improved compared to ferulic acid (FA) as the reaction class changes from low to medium. This attributed to the strong hydrogen abstraction occurred in the PILs. Furthermore, these PILs were found to have a good kinetic behavior compared to FA due to the high rate constant (k2) (164.17, 242.84 and 244.73 M-1 s-1, respectively). The alkyl chain length and more alkyl substituents on the nitrogen atom of cation were believed to reduce the cation-anion interaction and speed up the hydrogen atom transfer (HAT) and electron transfer (ET) mechanisms; hence, increased rate constant was observed leading to a strong antioxidant activity of the synthesized PILs.

Methyl oleate deoxygenation for production of diesel fuel aliphatic hydrocarbons over Pd/SBA-15 catalysts.

BACKGROUND: Catalytic deoxygenation is a prominent process for production of renewable fuels from vegetable oil. In this work, deoxygenation of technical grade methyl oleate to diesel fuel aliphatic hydrocarbons (C15 - C18) is evaluated with several parameters including temperature, hydrogen pressure and reaction time in a stirred batch reactor over Pd/SBA-15 catalysts. RESULTS: Two different SBA-15 morphologies i.e. spherelike and necklacelike structures have been synthesize as supports for Pd active metal. It is found that Pd dispersion on necklacelike SBA-15 is higher than that of spherelike SBA-15. Notably, higher Pd dispersion on necklacelike SBA-15 provides significant deoxygenation efficiency as compared to Pd/SBA-15-spherelike. Results show that H2 pressures greatly determine the total ester conversion and selectivity to C15 - C18 aliphatic hydrocarbons. Total ester conversions with 55< selectivity to n-heptadecane are achieved using Pd/SBA-15-necklacelike at 270°C and 60 bar H2 pressure within 6 h reaction time. Gas phase study reveals that formation of C17 is generated via indirect decarbonylation when the reaction time is prolonged. CONCLUSIONS: Pd/SBA-15-necklacelike catalyst exhibits good catalytic performance with high selectivity to diesellike aliphatic hydrocarbons (C15 - C18). The physicochemical properties of the Pd supported on different SBA-15 morphologies influence the deoxygenation activity of the catalysts. Furthermore, the reaction pathways are governed by the H2 pressure as well as reaction duration.

Gasifier selection, design and gasification of oil palm fronds with preheated and unheated gasifying air.

Oil palm frond biomass is abundantly available in Malaysia, but underutilized. In this study, gasifiers were evaluated based on the available literature data and downdraft gasifiers were found to be the best option for the study of oil palm fronds gasification. A downdraft gasifier was constructed with a novel height adjustment mechanism for changing the position of gasifying air and steam inlet. The oil palm fronds gasification results showed that preheating the gasifying air improved the volumetric percentage of H(2) from 8.47% to 10.53%, CO from 22.87% to 24.94%, CH(4) from 2.02% to 2.03%, and higher heating value from 4.66 to 5.31 MJ/Nm(3) of the syngas. In general, the results of the current study demonstrated that oil palm fronds can be used as an alternative energy source in the energy diversification plan of Malaysia through gasification, along with, the resulting syngas quality can be improved by preheating the gasifying air.