The combination of world population and the third industrial revolution led to high demand for fuels. On the other hand, the decrease of global fossil 8fuels deposits and the environmental air pollution caused by these fuels has compounded the challenges the world faces due to its need for energy. Therefore, new forms of environmentally friendly and renewable fuels such as biodiesel are needed. The primary analytical techniques for methanolysis yield monitoring have been chromatography and spectroscopy, these methods have been proven reliable but are more demanding, costly and do not provide real-time monitoring. In this work, the in situ monitoring of biodiesel from sunflower oil using FTIR (Fourier Transform Infrared) has been studied; the study was performed using EasyMax Mettler Toledo reactor equipped with a DiComp (Diamond) probe. The quantitative monitoring of methanolysis was performed by building a quantitative model with multivariate calibration using iC Quant module from iC IR 7.0 software. 15 samples of known concentrations were used for the modelling which were taken in duplicate for model calibration and cross-validation, data were pre-processed using mean centering and variance scale, spectrum math square root and solvent subtraction. These pre-processing methods improved the performance indexes from 7.98 to 0.0096, 11.2 to 3.41, 6.32 to 2.72, 0.9416 to 0.9999, RMSEC, RMSECV, RMSEP and R2Cum, respectively. The R2 value of 1 (training), 0.9918 (test), 0.9946 (cross-validation) indicated the fitness of the model built. The model was tested against univariate model; small discrepancies were observed at low concentration due to unmodelled intermediates but were quite close at concentrations above 18%. The software eliminated the complexity of the Partial Least Square (PLS) chemometrics. It was concluded that the model obtained could be used to monitor methanol of sunflower oil at industrial and lab scale.
Protorhus longifolia is known as a medicinal plant that has been used traditionally to treat various ailments such as hemiplegic paralysis, blood clotting related diseases, diarrhoea, heartburn, etc. The study reports a High-Performance Thin Layer Chromatography (HPTLC) fingerprint profile of Protorhus longifolia methanolic extract and its qualitative analysis of gallic acid, rutin, and quercetin. HPTLC analysis was achieved using CAMAG HPTLC system equipped with CAMAG automatic TLC sampler 4, CAMAG Automatic Developing Chamber 2 (ADC2), CAMAG visualizer 2, CAMAG Thin Layer Chromatography (TLC) scanner and visionCATS CAMAG HPTLC software. Mobile phase comprising toluene, ethyl acetate, formic acid (21:15:3) was used for qualitative analysis of gallic acid and revealed eight peaks while the mobile phase containing ethyl acetate, water, glacial acetic acid, formic acid (100:26:11:11) for qualitative analysis of rutin and quercetin revealed six peaks. HPTLC sillica gel 60 F254 glass plates (10 × 10) were used as the stationary phase. Gallic acid was detected at the Rf = 0.35; while rutin and quercetin were not evident in the extract. Further studies will be performed to quantify gallic acid in Protorhus longifolia leaves and also identify other biomarkers.
Thermochemical energy storage (TCES), as a long-term and lossless energy storage principle, provides a contribution for the reduction of greenhouse emissions of mobile applications, such as passenger vehicles with an internal combustion engine. A prototype of a TCES system, based on reversible sorption reactions of LiBr composite and methanol has been designed at Vienna University of Technology. In this paper, the selection of reactive and inert carrier materials as well as the design of heat exchangers (reactor vessel and evapo-condenser) was reviewed and the cycle stability under real operating conditions was investigated. The performance of the developed system strongly depends on the environmental temperatures, to which the reactor vessel and evapo-condenser are exposed during the phases of thermal conversion. For an integration of the system into mobile applications, the functionality of the designed prototype was proved in numerous conducted cycles whereby no adverse reactions were observed.
The swordfish (Xiphias gladius) is a large oceanic fish of high commercial value, which is widely distributed in waters of the world’s oceans. They are considered to be an important source of high quality proteins, vitamins and essential fatty acids, although only half of the population follows the recommendation of nutritionists to consume fish at least twice a week. Swordfish is consumed worldwide because of its low fat content and high protein content. It is generally sold as fresh, frozen, and as pieces or slices. The aim of this study was to evaluate the effect of salting and frying on the composition of the water-soluble vitamins (B2, B3, B9 and B12) and fat-soluble vitamins (A, D, and E) of swordfish. Three loins of swordfish from Pacific Ocean were analyzed. All the fishes had a weight between 50 and 70 kg and were transported to the laboratory frozen (-18 ºC). Before the processing, they were defrosted at 4 ºC. Each loin was sliced and salted in brine. After cleaning the slices, they were divided into portions (10×2 cm) and fried in olive oil. The identification and quantification of vitamins were carried out by high-performance liquid chromatography (HPLC), using methanol and 0.010% trifluoroacetic acid as mobile phases at a flow-rate of 0.7 mL min-1. The UV-Vis detector was used for the detection of the water- and fat-soluble vitamins (A and D), as well as the fluorescence detector for the detection of the vitamin E. During salting, water and fat-soluble vitamin contents remained constant, observing an evident decrease in the values of vitamin B2. The diffusion of salt into the interior of the pieces and the loss of constitution water that occur during this stage would be related to this significant decrease. In general, after frying water-soluble and fat-soluble vitamins showed a great thermolability with high percentages of retention with values among 50–100%. Vitamin B3 is the one that exhibited higher percentages of retention with values close to 100%. However, vitamin B9 presented the highest losses with a percentage of retention of less than 20%.
Colocasia esculenta leaves and roots are widely used in Asian countries, such as, India, Srilanka and Pakistan, as food and feed material. The root is high in carbohydrates and rich in zinc. The leaves and stalks are often traditionally preserved to be eaten in dry season. Leaf juice is stimulant, expectorant, astringent, appetizer, and otalgia. Looking at the medicinal uses of the plant leaves; phytochemicals were extracted from the plant leaves and were characterized using Fourier-transform infrared spectroscopy (FTIR) to find the functional groups. Phytochemical analysis of Colocasia esculenta (L.) leaf was studied using three solvents (methanol, chloroform, and ethanol) with soxhlet apparatus. Powder of the leaves was employed to obtain the extracts, which was qualitatively and quantitatively analyzed for phytochemical content using standard methods. Phytochemical constituents were abundant in the leave extract. Leaf was found to have various phytochemicals such as alkaloids, glycosides, flavonoids, terpenoids, saponins, oxalates and phenols etc., which could have lot of medicinal benefits such as reducing headache, treatment of congestive heart failure, prevent oxidative cell damage etc. These phytochemicals were identified using UV spectrophotometer and results were presented. In order to find the antioxidant activity of the extract, DPPH (2,2-diphenyl-1-picrylhydrazyl) method was employed using ascorbic acid as standard. DPPH scavenging activity of ascorbic acid was found to be 84%, whereas for ethanol it was observed to be 78.92%, for methanol: 76.46% and for chloroform: 72.46%. Looking at the high antioxidant activity, Colocasia esculenta may be recommended for medicinal applications. The characterizations of functional groups were analyzed using FTIR spectroscopy.
One dimensional pseudo-homogenous modeling has been performed for methanol steam reforming reactor. The results show that the models can well predict the industrial data. The reactor had minimum temperature along axial because of endothermic reaction. Hydrogen productions and temperature profiles along axial were investigated regarding operation conditions such as inlet mass flow rate and mass fraction of methanol, inlet temperature of external thermal oil. Low inlet mass flow rate of methanol, low inlet temperature, and high mass fraction of methanol decreased minimum temperature along axial. Low inlet mass flow rate of methanol, high mass fraction of methanol, and high inlet temperature of thermal oil made cold point forward. Low mass fraction, high mass flow rate, and high inlet temperature of thermal oil increased hydrogen production. One dimensional models can be a guide for industrial operation.
Alzheimer’s disease (AD) (a progressive neurodegenerative disorder) is mostly predominant cause of dementia in the elderly. Prolonging the function of acetylcholine by inhibiting both acetylcholinesterase and butyrylcholinesterase is most effective treatment therapy of AD. Traditionally Pterocarpus santalinus L. is widely known for its medicinal use. In this study, in vitro acetylcholinesterase inhibitory activity was investigated and methanolic extract of the plant showed significant activity. To confirm this activity (in vivo), learning and memory enhancing effects were tested in mice. For the test, memory impairment was induced by scopolamine (cholinergic muscarinic receptor antagonist). Anti-amnesic effect of the extract was investigated by the passive avoidance task in mice. The study also includes brain acetylcholinesterase activity. Results proved that scopolamine induced cognitive dysfunction was significantly decreased by administration of the extract solution, in the passive avoidance task and inhibited brain acetylcholinesterase activity. These results suggest that bark extract of Pterocarpus santalinus can be better option for further studies on AD via their acetylcholinesterase inhibitory actions.
SSZ-13 materials with different Si/Al ratio were prepared by varying the composition of aluminosilicate precursor solutions upon hydrothermal treatment at 150 °C. The Si/Al ratio of the initial system was systematically changed from 12.5 to infinity in order to study the limits of Al composition in precursor solutions for constructing CHA structure. The intermediates and final products were investigated by complementary techniques such as XRD, HRTEM, FESEM, and chemical analysis. NH3-TPD was used to study the Brønsted acidity of SSZ-13 samples with different Si/Al ratios. The effect of the Si/Al ratio on the precursor species, ultimate crystal size, morphology and yield was investigated. The results revealed that Al species determine the nucleation rate and the number of nuclei, which is tied to the morphology and yield of SSZ-13. The size of SSZ-13 increased and the yield decreased as the Si/Al ratio was improved. Varying Si/Al ratio of the initial system is a facile, commercially viable method of tailoring SSZ-13 crystal size and morphology. Furthermore, SSZ-13 materials with different Si/Al ratio were tested as catalysts for the methanol to olefins (MTO) reaction at 350 °C. SSZ-13 with the Si/Al ratio of 35 shows the best MTO catalytic performance.
Polyoxymethylene dimethyl ethers (PODEn) as clean diesel additive can improve the combustion efficiency and quality of diesel fuel and alleviate the problem of atmospheric pollution. Considering synthetic routes, PODE production from methanol and formaldehyde is regarded as the most economical and promising synthetic route. However, methanol used for synthesizing PODE can produce water, which causes the loss of active center of catalyst and hydrolysis of PODEn in the production process. Macroporous strong acidic cation exchange resin catalyst was prepared, which has comparative advantages over other common solid acid catalysts in terms of stability and catalytic efficiency for synthesizing PODE. Catalytic reactions were carried out under 353 K, 1 MPa and 3mL·gcat-1·h-1 in a fixed bed reactor. Methanol conversion and PODE3-6 selectivity reached 49.91% and 23.43%, respectively. Catalyst lifetime evaluation showed that resin catalyst retained its catalytic activity for 20 days without significant changes and catalytic activity of completely deactivated resin catalyst can basically return to previous level by simple acid regeneration. The acid exchange capacities of original and deactivated catalyst were 2.5191 and 0.0979 mmol·g-1, respectively, while regenerated catalyst reached 2.0430 mmol·g-1, indicating that the main reason for resin catalyst deactivation is that Brønsted acid sites of original resin catalyst were temporarily replaced by non-hydrogen ion cations. A separation process consisting of extraction and distillation for PODE3-6 product was designed for separation of water and unreacted formaldehyde from reactive mixture and purification of PODE3-6, respectively. The concentration of PODE3-6 in final product can reach up to 97%. These results indicate that the scale-up production of PODE3-6 from methanol and formaldehyde solution is feasible.
Biofuel production especially that of biodiesel has gained tremendous attention during the last decade due to environmental concerns and shortage in petroleum oil reservoir. This research aims to investigate the influences of operating parameters, such as the alcohol-to-oil molar ratio (4:1, 6:1, and 9:1) and the amount of catalyst (1, 1.5, and 2 wt.%) on the trans esterification of refined palm oil (RPO) in a medium-scale oscillatory baffle reactor. It has been shown that an increase in the methanol-to-oil ratio resulted in an increase in fatty acid methyl esters (FAMEs) content. The amount of catalyst has an insignificant effect on the FAMEs content. Engine testing was performed on B0 (100 v/v% diesel) and blended fuel or B50 (50 v/v% diesel). Combustion of B50 was found to give lower torque compared to pure diesel. Exhaust gas from B50 was found to contain lower concentration of CO and CO2.
The current study investigated the effect of catalyst ratio and methanol to oil ratio on biodiesel production by using central composite design. Biodiesel was produced by transesterification using sodium hydroxide as a homogeneous catalyst, a laboratory scale reactor consisting of flat bottom flask mounts with a reflux condenser and a heating plate was used to produce biodiesel. Key parameters, including, time, temperature and mixing rate were kept constant at 60 minutes, 60 oC and 600 RPM, respectively. From the results obtained, it was observed that the biodiesel yield depends on catalyst ratio and methanol to oil ratio. The highest yield of 50.65% was obtained at catalyst ratio of 0.5 wt.% and methanol to oil mole ratio 10.5. The analysis of variances of biodiesel yield showed the R Squared value of 0.8387. A quadratic mathematical model was developed to predict the biodiesel yield in the specified parameters ranges.
Methanol-to-propylene conversion was carried out in a continuous-flow fixed-bed reactor over nano-sized HZSM-5 zeolites. The HZSM-5 catalysts were synthesized with different Si/Al ratio and silicon sources, and treated with NaOH. The structural property, morphology, and acidity of catalysts were measured by XRD, N2 adsorption, FE-SEM, TEM, and NH3-TPD. The results indicate that the increment of Si/Al ratio decreased the acidity of catalysts and then improved propylene selectivity, while silicon sources had slight impact on the acidity but affected the product distribution. The desilication after alkali treatment could increase intracrystalline mesopores and enhance propylene selectivity.
Herbal essential oil and extracts are a good source of natural antioxidants and antimicrobial compounds. Hypericum is one of the potential sources of these compounds. In this study, the antioxidant and antimicrobial activity of essential oil and aqueous, methanol, ethanol, ethyl acetate and acetone extract of Hypericum scabrum was assessed. Flowers of Hypericum scabrum were collected from the surrounding mountains of Hamadan province and after drying in the shade, the essential oil of the plant was extracted by Clevenger and water, methanol, ethanol, ethyl acetate and acetone extract was obtained by maceration method. Essential oil compounds were identified using the GC-Mass. The Folin-Ciocalteau and aluminum chloride (AlCl3) colorimetric method was used to measure the amount of phenolic acid and flavonoids, respectively. Antioxidant activity was evaluated using DPPH and FRAP. The minimum inhibitory concentration (MIC) and the minimum bacterial/fungicide concentration (MBC/MFC) of essential oil and extracts were evaluated against Staphylococcus aureus, Bacillus cereus, Pseudomonas aeruginosa, Salmonella typhimurium, Aspergillus flavus and Candida albicans. The essential oil yield of was 0.35%, the lowest and highest extract yield was related to ethyl acetate and water extract. The most component of essential oil was α-Pinene (46.35%). The methanol extracts had the highest phenolic acid (95.65 ± 4.72 µg galic acid equivalent/g dry plant) and flavonoids (25.39 ± 2.73 µg quercetin equivalent/g dry plant). The percentage of DPPH radical inhibition showed positive correlation with concentrations of essential oil or extract. The methanol and ethanol extract had the highest DDPH radical inhibitory. Essential oil and extracts of Hypericum had antimicrobial activity against the microorganisms studied in this research. The MIC and MBC values for essential oils were in the range of 25-25.6 and 25-50 μg/mL, respectively. For the extracts, these values were 1.5625-100 and 3.125-100 μg/mL, respectively. Methanol extracts had the highest antimicrobial activity. Essential oil and extract of Hypericum scabrum, especially methanol extract, have proper antimicrobial and antioxidant activity, and it can be used to control the oxidation and inhibit the growth of pathogenic and spoilage microorganisms. In addition, it can be used as a substitute for synthetic antioxidant and antimicrobial compounds.
An impetus towards green consumerism and implementation of sustainable techniques, consumption of natural products and utilization of environment friendly techniques have gained accelerated acceptance. Butein, a natural colorant, has many medicinal properties apart from its use in dyeing industries. Extraction of butein from the flowers of flame of forest was carried out using ultrasonication bath. Solid loading (2-6 g), extraction time (30-50 min), volume of solvent (30-50 mL) and types of solvent (methanol, ethanol and water) have been studied to maximize the yield of butein using the Taguchi method. The highest yield of butein 4.67% (w/w) was obtained using 4 g of plant material, 40 min of extraction time and 30 mL volume of methanol as a solvent. The present method provided a greater reduction in extraction time compared to the conventional method of extraction. Hence, the outcome of the present investigation could further be utilized to develop the method at a higher scale.
The catalytic oxidation of CO and volatile organic compounds (VOCs) is considered as one of the most efficient ways to reduce harmful emissions from various chemical industries. The effectiveness of gold-based catalysts for many reactions of environmental significance was proven during the past three decades. The aim of this work was to combine the favorable features of Au and Cu-Ce mixed oxides in the design of new catalytic materials of improved efficiency and economic viability for removal of air pollutants in waste gases from formaldehyde production. Supported oxides of copper and cerium with Cu: Ce molar ratio 2:1 and 1:5 were prepared by wet impregnation of g-alumina. Gold (2 wt.%) catalysts were synthesized by a deposition-precipitation method. Catalysts characterization was carried out by texture measurements, powder X-ray diffraction, temperature programmed reduction and electron paramagnetic resonance spectroscopy. The catalytic activity in the oxidation of CO, CH3OH and (CH3)2O was measured using continuous flow equipment with fixed bed reactor. Both Cu-Ce/alumina samples demonstrated similar catalytic behavior. The addition of gold caused significant enhancement of CO and methanol oxidation activity (100 % degree of CO and CH3OH conversion at about 60 and 140 oC, respectively). The composition of Cu-Ce mixed oxides affected the performance of gold-based samples considerably. Gold catalyst on Cu-Ce/γ-Al2O3 1:5 exhibited higher activity for CO and CH3OH oxidation in comparison with Au on Cu-Ce/γ-Al2O3 2:1. The better performance of Au/Cu-Ce 1:5 was related to the availability of highly dispersed gold particles and copper oxide clusters in close contact with ceria.
This study aimed to investigate the effect of aggressive environment on the flexural properties of halloysite nanotubes-polyester nanocomposites. Results showed that the addition of halloysite nanotubes into polyester matrix was found to improve flexural properties of the nanocomposites in dry condition and after water-methanol exposure. Significant increase in surface roughness was also observed and measured by Alicona Infinite Focus optical microscope.
Carbon dioxide is highly thermochemical stable molecules where it is very difficult to activate the molecule and achieve higher catalytic conversion into alcohols or other hydrocarbon compounds. In this paper, series of the bimetallic Cu/ZnO-based catalyst supported by SBA-15 were systematically prepared via impregnation technique with different Cu: Zn ratio for hydrogenation of CO2 to methanol. The synthesized catalysts were characterized by transmission electron microscopy (TEM), temperature programmed desorption, reduction, oxidation and pulse chemisorption (TPDRO), and surface area determination was also performed. All catalysts were tested with respect to the hydrogenation of CO2 to methanol in microactivity fixed-bed reactor at 250oC, 2.25 MPa, and H2/CO2 ratio of 3. The results demonstrate that the catalytic structure, activity, and methanol selectivity was strongly affected by the ratio between Cu: Zn, Where higher catalytic activity of 14 % and methanol selectivity of 92 % was obtained over Cu/ZnO-SBA-15 catalyst with Cu:Zn ratio of 7:3 wt. %. Comparing with the single catalyst, the synergetic between Cu and Zn provides additional active sites to adsorb more H2 and CO2 and accelerate the CO2 conversion, resulting in higher methanol production under mild reaction conditions.
A systematic study was conducted to explore the photocatalytic reduction of carbon dioxide (CO2) into methanol on TiO2 loaded copper ferrite (CuFe2O4) photocatalyst under visible light irradiation. The phases and crystallite size of the photocatalysts were characterized by X-ray diffraction (XRD) and it indicates CuFe2O4 as tetragonal phase incorporation with anatase TiO2 in CuFe2O4/TiO2 hetero-structure. The XRD results confirmed the formation of spinel type tetragonal CuFe2O4 phases along with predominantly anatase phase of TiO2 in the CuFe2O4/TiO2 hetero-structure. UV-Vis absorption spectrum suggested the formation of the hetero-junction with relatively lower band gap than that of TiO2. Photoluminescence (PL) technique was used to study the electron–hole (e−/h+) recombination process. PL spectra analysis confirmed the slow-down of the recombination of electron–hole (e−/h+) pairs in the CuFe2O4/TiO2 hetero-structure. The photocatalytic performance of CuFe2O4/TiO2 was evaluated based on the methanol yield with varying amount of TiO2 over CuFe2O4 (0.5:1, 1:1, and 2:1) and changing light intensity. The mechanism of the photocatalysis was proposed based on the fact that the predominant species of CO2 in aqueous phase were dissolved CO2 and HCO3- at pH ~5.9. It was evident that the CuFe2O4 could harvest the electrons under visible light irradiation, which could further be injected to the conduction band of TiO2 to increase the life time of the electron and facilitating the reactions of CO2 to methanol. The developed catalyst showed good recycle ability up to four cycles where the loss of activity was ~25%. Methanol was observed as the main product over CuFe2O4, but loading with TiO2 remarkably increased the methanol yield. Methanol yield over CuFe2O4/TiO2 was found to be about three times higher (651 μmol/gcat L) than that of CuFe2O4 photocatalyst. This occurs because the energy of the band excited electrons lies above the redox potentials of the reaction products CO2/CH3OH.
Microalgae are tiny photosynthetic plants. Nowadays, microalgae are being used as nutrient-dense foods and sources of fine chemicals. They have significant amounts of lipid, carotenoids, vitamins, protein, minerals, chlorophyll, and pigments. Oil extraction from algae is a hotly debated topic currently because introducing an efficient method could decrease the process cost. This can determine the sustainability of algae-based foods. Scientific research works show that solvent extraction using chloroform/methanol (2:1) mixture is one of the efficient methods for oil extraction from algal cells, but both methanol and chloroform are toxic solvents, and therefore, the extracted oil will not be suitable for food application. In this paper, the effect of two food grade solvents (hexane and hexane/ isopropanol) on oil extraction yield from microalgae Dunaliella sp. was investigated and the results were compared with chloroform/methanol (2:1) extraction yield. It was observed that the oil extraction yield using hexane, hexane/isopropanol (3:2) and chloroform/methanol (2:1) mixture were 5.4, 13.93, and 17.5 (% w/w, dry basis), respectively. The fatty acid profile derived from GC illustrated that the palmitic (36.62%), oleic (18.62%), and stearic acids (19.08%) form the main portion of fatty acid composition of microalgae Dunalliela sp. oil. It was concluded that, the addition of isopropanol as polar solvent could increase the extraction yield significantly. Isopropanol solves cell wall phospholipids and enhances the release of intercellular lipids, which improves accessing of hexane to fatty acids.
In the work presented here, nitrogen-doped graphene materials were synthesized and used as metal-free electrocatalysts for oxygen reduction reaction (ORR) under alkaline conditions. Paraphenylenediamine was used as N precursor. The N-doped graphene was synthesized under hydrothermal treatment at 200°C. All the materials have been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Transmission electron microscopy (TEM) and X-ray photo-electron spectroscopy (XPS). Moreover, for electrochemical evaluation of samples, Rotating Disk electrode (RDE) and Cyclic Voltammetry techniques (CV) were employed. The resulting material exhibits an outstanding catalytic activity for the oxygen reduction reaction (ORR) as well as excellent resistance towards methanol crossover effects, indicating their promising potential as ORR electrocatalysts for alkaline fuel cells.
Carbon dioxide (CO2) emission to the environment is inevitable which is responsible for global warming. Photocatalytic reduction of CO2 to fuel, such as methanol, methane etc. is a promising way to reduce greenhouse gas CO2 emission. In the present work, Bi2S3/CdS was synthesized as an effective visible light responsive photocatalyst for CO2 reduction into methanol. The Bi2S3/CdS photocatalyst was prepared by hydrothermal reaction. The catalyst was characterized by X-ray diffraction (XRD) instrument. The photocatalytic activity of the catalyst has been investigated for methanol production as a function of time. Gas chromatograph flame ionization detector (GC-FID) was employed to analyze the product. The yield of methanol was found to increase with higher CdS concentration in Bi2S3/CdS and the maximum yield was obtained for 45 wt% of Bi2S3/CdS under visible light irradiation was 20 μmole/g. The result establishes that Bi2S3/CdS is favorable catalyst to reduce CO2 to methanol.