Liquid-liquid phase equilibria of aqueous biphasic systems based on glycerol formal:Application on tetracycline recovery from water

Biopharmaceuticals are commonly present in relatively low concentrations in aqueous solutions, making their detection and purification detrimental. In this work, we used novel aqueous biphasic systems based on glycerol formal (GF) to extract an important antibiotic - tetracycline. We report cloud points (solubility curve) and tie-lines for three ternary systems, containing GF, water, and inorganic salt (either K3PO4, K2HPO4, or K2CO3) at constant temperature of 298 K and at 0.1 MPa. The tie-line data of these ternary systems were correlated using the nonrandom two-liquid model, and binary interaction parameters of activity coefficients were estimated. The experimental and correlated tie-line data were compared in terms of average root-mean-square deviation and showed satisfactory agreements. The partition coefficients of tetracycline between two phases were measured, and corresponding extraction efficiencies were calculated. The maximum value of partition coefficient was 1551 for the system containing K3PO4, followed by values of 1145 and 927 for systems containing K2CO3 and K2HPO4, respectively. The calculated extraction efficiencies were very high - greater than 98.8%, demonstrating high potential for using aqueous biphasic systems based on GF for separation and purification processes

Process and Energy Intensification of Glycerol Carbonate Production from Glycerol and Dimethyl Carbonate in the Presence of Eggshell-Derived CaO Heterogeneous Catalyst

The process and energy intensifications for the synthesis of glycerol carbonate (GC) from glycerol and dimethyl carbonate (DMC) using an eggshell-derived CaO heterogeneous catalyst were investigated. The transesterification reaction between glycerol and DMC was typically limited by mass transfer because of the immiscible nature of the reactants. By varying the stirring speed, it was observed that the mass transfer limitation could be neglected at 800 rpm. The presence of the CaO solid catalyst made the mass transport-limited reaction process more prominent. Mass transfer intensification using a simple kitchen countertop blender as an alternative to overcome the external mass transfer limitation of a typical magnetic stirrer was demonstrated. A lower amount of the catalyst and a shorter reaction time were required to achieve 93% glycerol conversion or 91% GC yield, and the turnover frequency (TOF) increased almost 5 times from 1.5 to 7.2 min−1 when using a conventional magnetic stirrer and countertop blender, respectively. In addition, using a simple kitchen countertop blender with 7200 rpm, the reaction temperature of 60 °C could be reached within approximately 3 min without the need of a heating unit. This was the result of the self-frictional heat generated by the high-shear blender. This was considered to be heat transfer intensification, as heat was generated locally (in situ), offering a higher homogeneity distribution. Meanwhile, the trend toward energy intensification was promising as the yield efficiency increased from 0.064 to 2.391 g/kJ. A comparison among other process intensification techniques, e.g., microwave reactor, ultrasonic reactor, and reactive distillation was also rationalized

Fungal fermented palm kernel expeller as feed for black soldier fly larvae in producing protein and biodiesel

Being the second-largest country in the production of palm oil, Malaysia has a massive amount of palm kernel expeller (PKE) leftover. For that purpose, black soldier fly larvae (BSFL) are thus employed in this study to valorize the PKE waste. More specifically, this work elucidated the effects of the pre-fermentation of PKE via different amounts of Rhizopus oligosporus to enhance PKE palatability for the feeding of BSFL. The results showed that fermentation successfully enriched the raw PKE and thus contributed to the better growth of BSFL. BSFL grew to be 34% heavier at the optimum inoculum volume of 0.5 mL/10 g dry weight of PKE as compared to the control. Meanwhile, excessive fungal inoculum induced competition between BSFL and R. oligosporus, resulting in a reduction in BSFL weight. Under optimum feeding conditions, BSFL also registered the highest lipid yield (24.7%) and protein yield (44.5%). The biodiesel derived from BSFL lipid had also shown good compliance with the European biodiesel standard EN 14214. The high saturated fatty acid methyl esters (FAMEs) content (C12:0, C14:0, C16:0) in derived biodiesel made it highly oxidatively stable. Lastly, the superior degradation rate of PKE executed by BSFL further underpinned the sustainable conversion process in attaining valuable larval bioproducts

Comprehensive Review on Potential Contamination in Fuel Ethanol Production with Proposed Specific Guideline Criteria

Ethanol is a promising biofuel that can replace fossil fuel, mitigate greenhouse gas (GHG) emissions, and represent a renewable building block for biochemical production. Ethanol can be produced from various feedstocks. First-generation ethanol is mainly produced from sugar- and starch-containing feedstocks. For second-generation ethanol, lignocellulosic biomass is used as a feedstock. Typically, ethanol production contains four major steps, including the conversion of feedstock, fermentation, ethanol recovery, and ethanol storage. Each feedstock requires different procedures for its conversion to fermentable sugar. Lignocellulosic biomass requires extra pretreatment compared to sugar and starch feedstocks to disrupt the structure and improve enzymatic hydrolysis efficiency. Many pretreatment methods are available such as physical, chemical, physicochemical, and biological methods. However, the greatest concern regarding the pretreatment process is inhibitor formation, which might retard enzymatic hydrolysis and fermentation. The main inhibitors are furan derivatives, aromatic compounds, and organic acids. Actions to minimize the effects of inhibitors, detoxification, changing fermentation strategies, and metabolic engineering can subsequently be conducted. In addition to the inhibitors from pretreatment, chemicals used during the pretreatment and fermentation of byproducts may remain in the final product if they are not removed by ethanol distillation and dehydration. Maintaining the quality of ethanol during storage is another concerning issue. Initial impurities of ethanol being stored and its nature, including hygroscopic, high oxygen and carbon dioxide solubility, influence chemical reactions during the storage period and change ethanol’s characteristics (e.g., water content, ethanol content, acidity, pH, and electrical conductivity). During ethanol storage periods, nitrogen blanketing and corrosion inhibitors can be applied to reduce the quality degradation rate, the selection of which depends on several factors, such as cost and storage duration. This review article sheds light on the techniques of control used in ethanol fuel production, and also includes specific guidelines to control ethanol quality during production and the storage period in order to preserve ethanol production from first-generation to second-generation feedstock. Finally, the understanding of impurity/inhibitor formation and controlled strategies is crucial. These need to be considered when driving higher ethanol blending mandates in the short term, utilizing ethanol as a renewable building block for chemicals, or adopting ethanol as a hydrogen carrier for the long-term future, as has been recommended

Synthesis of Titania/Titanate Nanostructures for Photocatalytic Applications

Sodium titanate nanoribbons and nanotubes were synthesised by hydrothermally ageing Aeroxide P25 in 10M NaOH at temperatures between 150 and 200°C. The Na1.48H0.52Ti3O7 nanoribbons comprised a layered TiO6 nanosheet framework with sodium and hydrogen cations interspersed between the sheets. Nanoribbon/nanosheet formation occurred via an amorphous (Ti-O-Na) intermediate phase. At milder temperatures (i.e. 150°C), the kinetics of nanosheet formation are slow enough to allow for their rolling up leading to nanotube formation. Acid washing converted the structure into hydrogen titanate (H2Ti3O7) by ion-exchange and provided uniform nanoribbons and nanotubes.Heat treatment of hydrogen titanate transformed nanotubes to anatase, while nanoribbon transformation to anatase occurred via a TiO2(B) intermediate phase. The enhanced stability provided by the nanoribbon architecture preserved a dominant {010} crystal facet at temperatures higher than 700°C. Nanotube thermal stability was improved by nitric acid treatment. Methanol and oxalic acid photodegradation performance was the highest at calcination temperatures of 500°C for nanotubes and 800°C for nanoribbons. The nanotube optimum represented a transition between the dominance of surface area and crystal phase, while nanoribbon performance was governed primarily by crystal phase. Despite both nanostructures producing particles with similar physical characteristics when calcined at 800°C the particles originating from the nanoribbons exhibited superior photoactivity. This difference was attributed to a greater percentage of {010} crystal facet in these particles which is beneficial for hydroxyl radical generation.The photocatalytic activity of Na1.48H0.52Ti3O7, Na2Ti6O13, H2Ti3O7 nanoribbons and anatase TiO2 nanorods were compared for water splitting, oxalic acid photodegradation and H2/O2 generation using sacrificial agents. The intrinsic properties of the materials affected their performance depending on the particular reaction. The Na2Ti6O13, in the presence of RuO2 co-catalyst, outperformed the TiO2, for the water splitting reaction, generating over 10 times more H2/O2. This derived from their tunnel-like structure which provided better electron/hole separation when compared with TiO2. However, the efficient holes and electrons scavenging in the presence of sacrificial agents overwhelmed the tunnel-like structure effect. In this case photoactivity was governed by the crystal structure: TiO2>Na2Ti6O13>H2Ti3O7~Na1.48H0.52Ti3O7 and by the band gap of the semiconductor which determined its capacity to absorb photons in producing electron/hole pairs

Comprehensive Review on Potential Contamination in Fuel Ethanol Production with Proposed Specific Guideline Criteria

Ethanol is a promising biofuel that can replace fossil fuel, mitigate greenhouse gas (GHG) emissions, and represent a renewable building block for biochemical production. Ethanol can be produced from various feedstocks. First-generation ethanol is mainly produced from sugar- and starch-containing feedstocks. For second-generation ethanol, lignocellulosic biomass is used as a feedstock. Typically, ethanol production contains four major steps, including the conversion of feedstock, fermentation, ethanol recovery, and ethanol storage. Each feedstock requires different procedures for its conversion to fermentable sugar. Lignocellulosic biomass requires extra pretreatment compared to sugar and starch feedstocks to disrupt the structure and improve enzymatic hydrolysis efficiency. Many pretreatment methods are available such as physical, chemical, physicochemical, and biological methods. However, the greatest concern regarding the pretreatment process is inhibitor formation, which might retard enzymatic hydrolysis and fermentation. The main inhibitors are furan derivatives, aromatic compounds, and organic acids. Actions to minimize the effects of inhibitors, detoxification, changing fermentation strategies, and metabolic engineering can subsequently be conducted. In addition to the inhibitors from pretreatment, chemicals used during the pretreatment and fermentation of byproducts may remain in the final product if they are not removed by ethanol distillation and dehydration. Maintaining the quality of ethanol during storage is another concerning issue. Initial impurities of ethanol being stored and its nature, including hygroscopic, high oxygen and carbon dioxide solubility, influence chemical reactions during the storage period and change ethanol’s characteristics (e.g., water content, ethanol content, acidity, pH, and electrical conductivity). During ethanol storage periods, nitrogen blanketing and corrosion inhibitors can be applied to reduce the quality degradation rate, the selection of which depends on several factors, such as cost and storage duration. This review article sheds light on the techniques of control used in ethanol fuel production, and also includes specific guidelines to control ethanol quality during production and the storage period in order to preserve ethanol production from first-generation to second-generation feedstock. Finally, the understanding of impurity/inhibitor formation and controlled strategies is crucial. These need to be considered when driving higher ethanol blending mandates in the short term, utilizing ethanol as a renewable building block for chemicals, or adopting ethanol as a hydrogen carrier for the long-term future, as has been recommended

Synthesis of glycerol carbonate from dimethyl carbonate and glycerol using CaO derived from eggshells

Waste eggshell is proposed as a highly active catalyst for glycerol carbonate production from dimethyl carbonate (DMC) and glycerol. The effect of reaction temperature, reaction time and catalyst loading on the reaction performance were investigated in order to find a suitable operating condition. CaO derived from waste eggshell exhibits catalytic activity comparable to commercial CaO. By using CaO eggshell, glycerol conversion of 96% can be achieved within 90 min of reaction time under 2.5:1 feed molar ratio of DMC to glycerol, 0.08 mole ratio of CaO to glycerol and reaction temperature of 60°C. The catalyst was examined by XRD, TGA/DSC, SEM, N2 adsorption-desorption and Hammett indicators method. Utilization of eggshell as a catalyst for glycerol carbonate production not only provides a cost-effective and value-added of waste eggshell as a green catalyst, but also decrease amount of waste and its treatment cost which is ecologically friendly

Synthesis of glycerol carbonate from dimethyl carbonate and glycerol using CaO derived from eggshells

Waste eggshell is proposed as a highly active catalyst for glycerol carbonate production from dimethyl carbonate (DMC) and glycerol. The effect of reaction temperature, reaction time and catalyst loading on the reaction performance were investigated in order to find a suitable operating condition. CaO derived from waste eggshell exhibits catalytic activity comparable to commercial CaO. By using CaO eggshell, glycerol conversion of 96% can be achieved within 90 min of reaction time under 2.5:1 feed molar ratio of DMC to glycerol, 0.08 mole ratio of CaO to glycerol and reaction temperature of 60°C. The catalyst was examined by XRD, TGA/DSC, SEM, N2 adsorption-desorption and Hammett indicators method. Utilization of eggshell as a catalyst for glycerol carbonate production not only provides a cost-effective and value-added of waste eggshell as a green catalyst, but also decrease amount of waste and its treatment cost which is ecologically friendly