Over the past decades, research efforts are being devoted into utilizing the biomass waste as a major source of green energy to maintain the economic, environmental, and social sustainability. Specifically, there is an emerging consensus on the significance of glycerol (an underutilised waste from biodiesel industry) as a cheap, non-toxic, and renewable source for valuable chemicals synthesis. There are numerous methods enacted to convert this glycerol waste to tartronic acid, mesoxalic acid, glyceraldehyde, dihydroxyacetone, oxalic acid and so on. Among these, the green electro-oxidation technique is one of the techniques that possesses potential for industrial application due to advantages such as non-toxicity process, fast response, and lower energy consumption. The current review covers the general understanding on commonly used techniques for alcohol (C1 & C2) conversion, with a specific insight on glycerol (C3) electro-oxidation (GOR). Since catalysts are the backbone of chemical reaction, they are responsible for the overall economy prospect of any processes. To this end, a comprehensive review on catalysts, which include noble metals, non-noble metals, and non-metals anchored over various supports are incorporated in this review. Moreover, a fundamental insight into the development of future electrocatalysts for glycerol oxidation along with products analysis is also presented.
Interest in biodiesel research has escalated over the years due to dwindling fossil fuel reserves. The implementation of a carbon-based solid acid catalyst in biodiesel production eradicates the separation problems associated with homogeneous catalysis. However, its application in the glycerol-free interesterification process for biodiesel production is still rarely being studied in the literature. In this study, novel environmentally benign catalysts were prepared from oil palm empty fruit bunch (OPEFB) derived activated carbon (AC) which is sustainable and low cost via direct sulfonation using concentrated sulfuric acid. The effects of synthesizing variables such as carbonization and sulfonation temperatures with different holding times towards the fatty acid methyl ester (FAME) yield in interesterification reaction with oleic acid and methyl acetate were investigated in detail. It was found that the optimum carbonization temperature and duration together with sulfonation temperature and duration were 600 °C, 3 h, 100 °C and 6 h, respectively. The catalyst possessed an amorphous structure with a high total acid density of 9.0 mmol NaOH g-1 due to the well-developed porous framework structure of the carbon support. Under these optimum conditions, the OPEFB derived solid acid catalyst recorded an excellent catalytic activity of 50.5% methyl oleate yield at 100 °C after 8 h with 50:1 methyl acetate to oleic acid molar ratio and 10 wt% catalyst dosage. The heterogeneous acid catalyst derived from OPEFB had shown promising properties that made them highly suitable for cost-effective and environmental-friendly glycerol-free biodiesel production.
Diacylglycerol (DAG) and monoacylglycerol (MAG) are two natural occurring minor components found in most edible fats and oils. These compounds have gained increasing market demand owing to their unique physicochemical properties. Enzymatic glycerolysis in solvent-free system might be a promising approach in producing DAG and MAG-enriched oil. Understanding on glycerolysis mechanism is therefore of great importance for process simulation and optimization. In this study, a commercial immobilized lipase (Lipozyme TL IM) was used to catalyze the glycerolysis reaction. The kinetics of enzymatic glycerolysis reaction between triacylglycerol (TAG) and glycerol (G) were modeled using rate equation with unsteady-state assumption. Ternary complex, ping-pong bi-bi and complex ping-pong bi-bi models were proposed and compared in this study. The reaction rate constants were determined using non-linear regression and sum of square errors (SSE) were minimized. Present work revealed satisfactory agreement between experimental data and the result generated by complex ping-pong bi-bi model as compared to other models. The proposed kinetic model would facilitate understanding on enzymatic glycerolysis for DAG and MAG production and design optimization of a pilot-scale reactor.
This study provides insight into the decolorization strategy for crude glycerol obtained from biodiesel production using waste cooking oil as raw material. A sequential procedure that includes physico-chemical treatment and adsorption using activated carbon from oil palm biomass was investigated. The results evidenced decolorization and enrichment of glycerol go hand in hand during the treatment, achieving >89% color removal and > 98% increase in glycerol content, turning the glycerol into a clear (colorless) solution. This is attributed to the complete removal of methanol, free fatty acids, and triglycerides, as well as 85% removal of water, and 93% removal of potassium. Properties of the resultant glycerol met the quality standard of BS 2621:1979. The economic aspects of the proposed methods are examined to fully construct a predesign budgetary estimation according to chemical engineering principles. The starting capital is proportionate to the number of physical assets to acquire where both entail a considerable cost at USD 13,200. Having the benefit of sizeable scale production, it reasonably reduces the operating cost per unit product. As productivity sets at 33 m3 per annum, the annual operating costs amount to USD 79,902 in glycerol decolorization. This is translatable to USD 5.38 per liter glycerol, which is ~69% lower compared to using commercial activated carbon.
This study investigated an innovative strategy of incorporating surfactants into alkaline-catalyzed glycerol pretreatment and enzymatic hydrolysis to improve lignocellulosic biomass (LCB) conversion efficiency. Results revealed that adding 40 mg/g PEG 4000 to the pretreatment at 195 °C obtained the highest glucose yield (84.6%). This yield was comparable to that achieved without surfactants at a higher temperature (240 °C), indicating a reduction of 18.8% in the required heat input. Subsequently, Triton X-100 addition during enzymatic hydrolysis of PEG 4000-assisted pretreated substrate increased glucose yields to 92.1% at 6 FPU/g enzyme loading. High-solid fed-batch semi-simultaneous saccharification and co-fermentation using this dual surfactant strategy gave 56.4 g/L ethanol and a positive net energy gain of 1.4 MJ/kg. Significantly, dual assistance with surfactants rendered 56.3% enzyme cost savings compared to controls without surfactants. Therefore, the proposed surfactant dual-assisted promising approach opens the gateway to economically viable enzyme-mediated LCB biorefinery.
The objective of this work was to develop a plastic film from food sources with excellent thermal, mechanical, and degradability performance. Corn starch (CS)/nata de coco (NDC) were hybridized with addition of glycerin as plasticizer at different weight ratio and weight percent, respectively. Sample analysis found that the hybridization of CS with NDC improved the film forming properties, mechanical and thermal, degradation properties, as well as hydrophobicity and solubility of the film up to 0.5:0.5 wt hybrid ratio. The properties of the films were highly affected by the homogeneity of the sample during hybridization, with high NDC amount (0.3:0.7 wt CS:NDC) showing poor hydrophobicity, and mechanical and thermal properties. The glycerin content, however, did not significantly affect the hydrophobicity, water solubility, and degradability properties of CS/NDC film. Hybridization of 0.5:0.5 wt CS/NDC with 2 phr glycerin provided the optimum Young's modulus (15.67 MPa) and tensile strength (1.67 MPa) properties.
The formation of 3-monochloropropane-1,2-diol (3-MCPD) esters in refined palm oil during deodorisation is attributed to the intrinsic composition of crude palm oil. Utilising D-optimal design, the effects of the degumming and bleaching processes on the reduction in 3-MCPD ester formation in refined palm oil from poor-quality crude palm oil were studied relative to the palm oil minor components that are likely to be their precursors. Water degumming remarkably reduced 3-MCPD ester formation by up to 84%, from 9.79 mg/kg to 1.55 mg/kg. Bleaching with synthetic magnesium silicate caused a further 10% reduction, to 0.487 mg/kg. The reduction in 3-MCPD ester formation could be due to the removal of related precursors prior to the deodorisation step. The phosphorus content of bleached palm oil showed a significant correlation with 3-MCPD ester formation.
The reduction of 3-monochloropropane-1,2-diol (3-MCPD) ester formation in refined palm oil was achieved by incorporation of additional processing steps in the physical refining process to remove chloroester precursors prior to the deodorization step. The modified refining process was optimized for the least 3-MCPD ester formation and acceptable refined palm oil quality using response surface methodology (RSM) with five processing parameters: water dosage, phosphoric acid dosage, degumming temperature, activated clay dosage, and deodorization temperature. The removal of chloroester precursors was largely accomplished by increasing the water dosage, while the reduction of 3-MCPD esters was a compromise in oxidative stability and color of the refined palm oil because some factors such as acid dosage, degumming temperature, and deodorization temperature showed contradictory effects. The optimization resulted in 87.2% reduction of 3-MCPD esters from 2.9 mg/kg in the conventional refining process to 0.4 mg/kg, with color and oil stability index values of 2.4 R and 14.3 h, respectively.
The influence of diacylglycerol (DAG) combined with polyglycerol polyricinoleate (PGPR) on the stability of water-in-oil (W/O) emulsions containing hydrogenated palm oil (HPO) was studied. Polarized light microscope revealed that DAG promoted HPO to crystallize at the water-oil interface, providing the combination of Pickering and network stabilization effects. It was proposed that the molecular compatibility of fatty acids in DAG with HPO accounted for the promotional effect. The interfacial crystallization of DAG together with the surface activity of PGPR led to the formation of emulsions with uniform small droplets and high freeze-thaw stability. Further exploration of physical properties indicated that the combination of DAG and PGPR dramatically improved the emulsion's viscoelasticity and obtained a larger deformation yield. Water droplets in DAG-based emulsions acted as active fillers to improve the network rigidity. Therefore, DAG is a promising material to be used as emulsifier to enhance the physical stability of W/O emulsions.
This study examines the effects of varying the concentrations of sorbitol (S) and glycerol (G) on the physical, morphological, thermal, and mechanical properties of Dioscorea hispida, starch-based films. In this context, the films of Dioscorea hispida starch were developed using solution casting technique with glycerol (G), sorbitol (S), and a mixture of sorbitol-glycerol (SG) as plasticizers at the ratios of 0, 30, 45, and 60 wt%. The films' moisture contents were increased when increasing the plasticizer contents. The tensile strengths were decreased, but elongations at break were increased; 7.38%-11.54% for G-plasticized films, 10.17%-15.76% for S-plasticized films, and 14.41%- 16.10% for SG-plasticized films with increasing plasticizer concentrations of the film samples. Varying plasticizer concentrations exhibited a minor effect on the S-plasticized film's thermal properties. Significant decrement in the glass transition temperatures of Dioscorea hispida starch films was observed when the plasticizer contents were raised from 30% to 60%. Significantly, the present work has shown that plasticized Dioscorea hispida starch can be considered a promising biopolymer for the applications of biodegradable films.
Oil-in-water (o/w) emulsion is utilized as an insecticide delivery system for mosquito control. However, evaporation inhibition adjuvant is needed to prevent fog drift, inhibit release of insecticidal actives and prolong suspension time. In the current study, we evaluated the effect of different short-chain alcohols, namely, propylene glycol, 1,3-propanediol, glycerol and crude glycerol, as adjuvants on the physicochemical properties of d-phenothrin o/w emulsion system. The bioactivity of optimized formulations containing 20 wt% glycerol (D1), 20 wt% propylene glycol (D2) and without added alcohol (negative control) were tested against larvae, pupae and adult Aedes aegypti (Ae. aegypti). It was found that propylene glycol produced smaller droplets at lower concentrations but poor long-term stability at higher concentrations, whereas glycerol had an appreciable effect on initial droplet size and stability with increasing concentration. According to the dose-response bioassays and room size chamber testing, the highest larvicidal, pupicidal and adulticidal activities were observed with D2, followed by D1 and negative control. Overall, the above study demonstrated improved emulsion stabilities and potency against Ae. aegypti larvae, pupae and adults using glycerol as adjuvant for effective mosquito control.
Comparative whole-genome sequencing enables the identification of specific mutations during adaptation of bacteria to new environments and allelic replacement can establish their causality. However, the mechanisms of action are hard to decipher and little has been achieved for epistatic mutations, especially at the metabolic level. Here we show that a strain of Escherichia coli carrying mutations in the rpoC and glpK genes, derived from adaptation in glycerol, uses two distinct metabolic strategies to gain growth advantage. A 27-bp deletion in the rpoC gene first increases metabolic efficiency. Then, a point mutation in the glpK gene promotes growth by improving glycerol utilization but results in increased carbon wasting as overflow metabolism. In a strain carrying both mutations, these contrasting carbon/energy saving and wasting mechanisms work together to give an 89% increase in growth rate. This study provides insight into metabolic reprogramming during adaptive laboratory evolution for fast cellular growth.
Deep eutectic solvent (DES) affinities with cellular membranes structures dictate the degree of cytotoxicity that results from these interactions. The physicochemical properties of choline chloride (ChCl)-DESs suggest non-negligible cytotoxicities that were attested by published researches. In this study, the profiles of novel N,N-diethylammonium chloride (DAC)-based-deep eutectic solvents (DESs) prepared with various hydrogen bond donors (urea, glycerol, ethylene glycol, malonic acid, and zinc chloride) were compared to those of ChCl-DESs by using HelaS3, AGS, MCF-7, and WRL-68 cancer cell lines. The molecular interactions between salts and cellular membranes were investigated to explain the observed cytotoxicity. The results show that ChCl-based DESs (279 ≤ IC50 ≥ 1260 mM) were less toxic than DAC-based DESs (37 ≤ IC50 ≥ 109 mM). COSMO-RS analysis emphasized the importance of salt hydrophobicity with regards to DESs cytotoxicity. Malonic acid increased hydrophobicity and cytotoxicity in general, thus highlighting the potential of ammonium salt-based DESs as anticancer agents.
Several binary and ternary medium- and long-chain triacylglycerol (MLCT)-enriched margarine formulations were examined for their solid fat content, heating profile, polymorphism and textural properties. MLCT feedstock was produced through enzymatic esterification of capric and stearic acids with glycerol. The binary formulations were produced by mixing MLCT feedstock blend (40%–90%) and palm olein (10%–60%) with 10% increments (w/w). Solid fat profiles of commercial margarines were used as a reference to determine the suitability of the formulations for margarine production. The solid fat content of the binary formulations of MO 82 and MO 91 (M, MLCT, O, palm olein) were similar to the commercial margarines at 25°C which met the basic requirement for efficient dough consistency. Ternary formulations using reduced MLCT feedstock blend proportion (from 80%–90% to 60%–70%) were also developed. The reduction of MLCT feedstock blend was
done as it had the highest production cost (3USD/kg) in comparison to palm olein (0.77USD/kg) and palm stearin (0.7USD/kg). The proportions of 5%–15% of palm stearin were substituted with palm olein in MO 64 and MO 73 (M, MLCT; O, palm olein) formulations with 5% increment (w/w). As a result, MOS 702010 and MOS 603010 (M, MLCT; O, palm olein; S, palm stearin) margarine formulations showed similar SFC % to the commercial margarines at 25ºC. These formulations were subsequently chosen to produce margarines. The onset melting and complete melting points of MLCT-enriched margarine formulations were high (51.04ºC –57.93ºC) due to the presence of a high amount of long chain saturated fatty acids. Most of the formulations showed β΄- crystals. MOS 702010 was selected as the best formulation due to values for textural parameters comparable (P
In this study, we developed a glycerol-mediated safe and facile method to synthesize colored titania nanoparticles (NPs) via solution route. Our method is considerably effective and greener than other options currently available. Colored titania NPs were produced by hydrolyzing TiCl4 precursor in aqueous solution containing different concentrations of glycerol (0.0, 1.163, 3.834, and 5.815 mol/L) and subsequent calcination at 300 °C for 1 h. Our results highlight firstly that glycerol-mediated synthesis is unlikely to affect the anatase crystalline structure of TiO2, and secondly, that it would lead to coloration, band gap narrowing, and a remarkable bathochromic redshift of the optical response of titania. More importantly, the synthesized colored titania have Ti3+ ions, which, at least in terms of our samples, is the major factor responsible for its coloration. These Ti3+ species could induce mid gap states in the band gap, which significantly improve the visible light absorption capability and photocatalytic performance of the colored titania. The photocatalytic experiments showed that the colored TiO2 NPs prepared in 1.163 mol/L aqueous glycerol solution displayed the best photocatalytic performance. Almost 48.17% of phenolic compounds and 62.18% of color were removed from treated palm oil mill effluent (POME) within 180 min of visible light irradiation.
This paper reports the effects of glyceryl ether specifically mono-tert-butoxypropanediol on oil in water emulsion system.
Based on 12 HLB value, screening for stable emulsions was carried out without the presence of glyceryl ether. A stable
emulsion was used as a control. Then the effects of glyceryl ether on the emulsion system were investigated. The emulsions
prepared were analyzed for stability, viscosity, pH value, particle size, in vitro dermal irritation potential, in vitro ocular
irritation potential and also moisturizing property. The incorporation of glycerol in the emulsion system was also done
for comparison. Emulsions with glyceryl ether showed lower viscosity values than emulsions with glycerol. Furthermore,
the emulsions also exhibited moisturizing property compared to the control emulsion. Glyceryl ether is suitable to be
used in cosmetic products which require reduced viscosity but retain its skin hydration property.
In recent years, increasing environmental concerns focused greater attention on the development of biodegradable materials. A thermoplastic starch derived from bioresources, sugar palm tree was successfully developed in the presence of biodegradable glycerol as a plasticizer. Sugar palm starch (SPS) was added with 15-40 w/w% of glycerol to prepare workable bioplastics and coded as SPS/G15, SPS/G20, SPS/G30 and SPS/G40. The samples were characterized for thermal properties, mechanical properties and moisture absorption on exposure to humidity were evaluated. Morphological studies through scanning electron microscopy (SEM) were used to explain the observed mechanical properties. Generally, the addition of glycerol decrease the transition temperature of plasticized SPS. The mechanical properties of plasticized SPS increase with the increasing of glycerol but up to 30 w/w%. Meanwhile, the water absorption of plasticized SPS decrease with increasing of glycerol.
Momordica charantia bioactive polysaccharide (MCBP) was used as an alternative source for the production of bio-based plastics (BPs) with choline chloride/glycerol-based deep eutectic solvent (DES) as a plasticizer. In this study, MCBP was initially extracted using 0.1 M citric acid at temperature 80 °C for 2 h, precipitated using ethanol, and then lyophilized. Subsequently, seven BPs were prepared: MCBP without plasticizer (MCBP), with 1% (w/w) of glycerol (MCBP-G), or with 1% (w/w) of DES at different choline chloride/glycerol molar ratios (i.e. 1.5:1, 1:1, 1:1.5, 1:2, and 1:3). The properties of these BPs were then investigated. Results showed that the tensile strains, stresses and moduli were in the range of 1.3-13.3%, 4.8-19.1 MPa and 132-2487 MPa, respectively. The melting temperatures were found in the range of 92.6-111.4 °C whereas the moisture absorptions and water vapour transmission rates (WVTR) of BPs were 1.4-6.5% and 3.6-5.4 mg/m2·s, respectively. The results also showed that these BPs exhibited bioactivities, such as microbial inhibitory activity (19.5-32.3 mm), free radical scavenging activity (10.3-18.3%) and ferric reducing antioxidant power (FRAP, 16.1-20.0 mM). In addition, it was observed that using DES as a plasticizer had improved the properties of BP, such as tensile strain (354.7-937.5%), melting temperature (4.6-20.3%), radical scavenging activity (0.6-88.6%), FRAP (0.9-18.7%) and antimicrobial activity (12.3-33.6%) compared to MCBP, due to the fact DES has caused different degrees of plasticization via hydrogen bonds and ionic bonds with the polymer chains, and induced a lower pH condition. Therefore, it was suggested that these BPs with DES could contribute to food preservation properties.
The presence of 3-monochloropropanediol esters (3-MCPDE), 2-monochloropropanediol esters (2-MCPDE) and glycidyl esters (GE) in infant formula products has raised serious concerns. They incorporate vegetable oils, particularly palm-based oils, which are well-known to contain large amounts of these process contaminants. An analysis was conducted on infant formula samples (n = 16) obtained from the Malaysian market to determine the levels of 3-MCPDE, 2-MCPDE and GE using gas chromatography-mass spectrometry (GC-MS). The method was validated, with a limit of quantification (LOQ) on instrument of 0.10 µg/g for all analytes. The median concentrations of 3-MCPDE, 2-MCPDE and GE in infant formula in this study were 0.008 µg/g, 0.003 µg/g and 0.002 µg/g respectively. The estimated dietary intakes calculated from consumption of infant formula show higher exposures to infants within the age group of 0 to 5 months, highest for GE (1.61 µg/kg bw/day), followed by 3-MCPDE (0.68 µg/kg bw/day) and 2-MCPDE (0.41 µg/kg bw/day) compared to the age group of 6 to 12 months. Only one sample, relating to GE exposure is a potential risk for both age groups with MOE value below 25,000.
Esters of 2- and 3-monochloropropanediol (2-MCPDE, 3-MCPDE) and glycidol (GE) are regarded as process contaminants that are found in refined vegetable oils and oil-based foods. Since glycerol is produced during fat splitting, saponification and biodiesel production, it is important to have methods for determining contaminants that might be formed during these processes. Due to the use of glycerol as a food additive, data on the presence of compounds of toxicological concern, including 3-MCPD, are of interest. This study focuses on modifying the indirect analysis of 2-MCPDE, 3-MCPDE and GE using GC-MS based on the AOCS Official Method Cd 29a-13, validating the modified method, and quantifying 2-MCPDE, 3-MCPDE and GE in glycerol. The AOCS Cd 29a-13 method was modified at the initial stage of sample preparation in which the targeted esters were extracted from glycerol by vortex-assisted extraction before sample analysis. This modification was performed based on the polarity of all compounds involved. The calibration functions for all analytes were fitted to linear regression with R2 above 0.99. Limits of detection (LOD) 0.02, 0.01 and 0.02 mg kg-1 were obtained for 2-MCPDE, 3-MCPDE and GE, respectively. Spiked glycerol with 3-MCPDE and 2-MCPDE (0.25, 0.51 and 1.01 mg kg-1) and GE (0.58, 1.16 and 2.32 mg kg-1) were used for recovery and precision measurements. Recoveries of 100-108%, 101-103%, and 93-99% were obtained for 2-MCPDE, 3-MCPDE and GE, respectively. Acceptable precision levels with relative standard deviations ranged from 3.3% to 8.3% were obtained for repeatability and intermediate precision. The validated method was successfully applied for the analysis of the target compounds in refined glycerol from commercial plants, which showed that 2-MCPDE, 3-MCPDE and GE levels in the analysed samples were below the detection limit.