In recent years, environmental problems caused by the use of fossil fuels and the depletion of petroleum reserves have driven the world to adopt biodiesel as an alternative energy source to replace conventional petroleum-derived fuels because of biodiesel's clean and renewable nature. Biodiesel is conventionally produced in homogeneous, heterogeneous, and enzymatic catalysed processes, as well as by supercritical technology. All of these processes have their own limitations, such as wastewater generation and high energy consumption. In this context, the membrane reactor appears to be the perfect candidate to produce biodiesel because of its ability to overcome the limitations encountered by conventional production methods. Thus, the aim of this paper is to review the production of biodiesel with a membrane reactor by examining the fundamental concepts of the membrane reactor, its operating principles and the combination of membrane and catalyst in the catalytic membrane. In addition, the potential of functionalised carbon nanotubes to serve as catalysts while being incorporated into the membrane for transesterification is discussed. Furthermore, this paper will also discuss the effects of process parameters for transesterification in a membrane reactor and the advantages offered by membrane reactors for biodiesel production. This discussion is followed by some limitations faced in membrane technology. Nevertheless, based on the findings presented in this review, it is clear that the membrane reactor has the potential to be a breakthrough technology for the biodiesel industry.
In recent years, carbon nanotubes have received widespread attention as promising carbon-based nanoelectronic devices. Due to their exceptional physical, chemical, and electrical properties, namely a high surface-to-volume ratio, their enhanced electron transfer properties, and their high thermal conductivity, carbon nanotubes can be used effectively as electrochemical sensors. The integration of carbon nanotubes with a functional group provides a good and solid support for the immobilization of enzymes. The determination of glucose levels using biosensors, particularly in the medical diagnostics and food industries, is gaining mass appeal. Glucose biosensors detect the glucose molecule by catalyzing glucose to gluconic acid and hydrogen peroxide in the presence of oxygen. This action provides high accuracy and a quick detection rate. In this paper, a single-wall carbon nanotube field-effect transistor biosensor for glucose detection is analytically modeled. In the proposed model, the glucose concentration is presented as a function of gate voltage. Subsequently, the proposed model is compared with existing experimental data. A good consensus between the model and the experimental data is reported. The simulated data demonstrate that the analytical model can be employed with an electrochemical glucose sensor to predict the behavior of the sensing mechanism in biosensors.
Structured lipid is a type of modified form of lipid that is "fabricated" with the purpose to improve the nutritional and functional properties of conventional fats and oils derived from animal and plant sources. Such healthier choice of lipid received escalating attention from the public for its capability to manage the rising prevalence of metabolic syndrome. Of which, medium-chain triacylglycerol (MCT) and medium-and long-chain triacylglycerol (MLCT) are the few examples of the "new generation" custom-made healthful lipids which are mainly composed of medium chain fatty acid (MCFA). MCT is made up exclusively of MCFA whereas MLCT contains a mixture of MCFA and long chain fatty acid (LCFA), respectively. Attributed by the unique metabolism of MCFA which is rapidly metabolized by the body, MCFA and MCT showed to acquire multiple physiological and functional properties in managing and reversing certain health disorders. Several chemically or enzymatically oils and fats modification processes catalyzed by a biological or chemical catalyst such as acidolysis, interesterification and esterification are adopted to synthesis MCT and MLCT. With their purported health benefits, MCT and MLCT are widely being used as nutraceutical in food and pharmaceutical sectors. This article aims to provide a comprehensive review on MCT and MLCT, with an emphasis on the basic understanding of its structures, properties, unique metabolism; the current status of the touted health benefits; latest routes of production; its up-to-date applications in the different food systems; relevant patents filed and its drawbacks.
In this study, biodiesel was produced from sludge palm oil (SPO) using tolune-4-sulfonic monohydrate acid (PTSA) as an acid catalyst in different dosages in the presence of methanol to convert free fatty acid (FFA) to fatty acid methyl ester (FAME), followed by a transesterification process using an alkaline catalyst. In the first step, acid catalyzed esterification reduced the high FFA content of SPO to less than 2% with the different dosages of PTSA. The optimum conditions for pretreatment process by esterification were 0.75% (w/w) dosage of PTSA to SPO, 10:1 M ratio, 60 °C temperature, 60 min reaction time and 400 rpm stirrer speed. The highest yield of biodiesel after transesterification and purification processes was 76.62% with 0.07% FFA and 96% ester content. The biodiesel produced was favorable as compared to EN 14214 and ASTM 6751 standard. This study shows a potential exploitation of SPO as a new feedstock for the production of biodiesel.
The first purification of the Mo-reducing enzyme from Serratia sp. strain DRY5 that is responsible for molybdenum reduction to molybdenum blue in the bacterium is reported. The monomeric enzyme has an apparent molecular weight of 105 kDalton. The isoelectric point of this enzyme was 7.55. The enzyme has an optimum pH of 6.0 and maximum activity between 25 and 35°C. The Mo-reducing enzyme was extremely sensitive to temperatures above 50°C (between 54 and 70°C). A plot of initial rates against substrate concentrations at 15 mM 12-MP registered a V max for NADH at 12.0 nmole Mo blue/min/mg protein. The apparent K m for NADH was 0.79 mM. At 5 mM NADH, the apparent V max and apparent K m values for 12-MP of 12.05 nmole/min/mg protein and 3.87 mM, respectively, were obtained. The catalytic efficiency (k cat/K m ) of the Mo-reducing enzyme was 5.47 M(-1) s(-1). The purification of this enzyme could probably help to solve the phenomenon of molybdenum reduction to molybdenum blue first reported in 1896 and would be useful for the understanding of the underlying mechanism in molybdenum bioremediation involving bioreduction.
Trimethylolpropane triesters are biodegradable synthetic lubricant base oil alternative to mineral oils, polyalphaolefins and diesters. These oils can be produced from trimethylolpropane (TMP) and fatty acid methyl esters via chemical or enzymatic catalyzed synthesis methods. In the present study, a commercial palm oil derived winter grade biodiesel (ME18) was evaluated as a viable and sustainable methyl ester source for the synthesis of high oleic trimethylolpropane triesters (HO-TMPTE). ME18 has fatty acid profile containing 86.8% oleic acid, 8.7% linoleic acid with the remaining minor concentration of palmitic acid, stearic acid and linolenic acid. It's high oleic property makes it superior to produce synthetic lubricant base oil that fulfills both the good low temperature property as well as good oxidative stability. The synthetic base oil produced had a viscosity of 44.3 mm(2)/s at 40°C meeting the needs for ISO 46 oils. It also exhibited an excellent viscosity index of 219 that is higher than some other commercial brands of trimethylolpropane trioleate. Properties of base oil such as cloud point, density, acid value, demulsibility and soap content were also examined. The oil was then used in the formulation of tapping oil and appraised in term of adaptability, stability and field test performance.
Single-walled carbon nanotubes (SWCNTs) were synthesized by catalytic chemical vapor deposition (CCVD) of ethanol (C2H5OH) over Fe-Mo-MgO catalyst by using argon as a carrier gas. The reaction conditions are important factors that influence the yield and quality of carbon nanotubes. The effects of temperature and flow rate of carrier gas were investigated to increase the yield of carbon nanotubes. The synthesized carbon nanotubes were characterized by scanning electron microscopy, transmission electron microscopy, X-Ray diffraction and thermo-gravimetric analysis. The results showed that the growth of carbon nanotubes was effectively influenced by the reaction ambience and the synthesis condition. The temperature and flow rate of carrier gas played a key role in the yield and quality of synthesized CNTs. The estimated yield of synthesized carbon nanotubes was almost over 70%.
Graphene (GR) and its derivatives are promising materials on the horizon of nanotechnology and material science and have attracted a tremendous amount of research interest in recent years. The unique atom-thick 2D structure with sp(2) hybridization and large specific surface area, high thermal conductivity, superior electron mobility, and chemical stability have made GR and its derivatives extremely attractive components for composite materials for solar energy conversion, energy storage, environmental purification, and biosensor applications. This review gives a brief introduction of GR's unique structure, band structure engineering, physical and chemical properties, and recent energy-related progress of GR-based materials in the fields of energy conversion (e.g., photocatalysis, photoelectrochemical water splitting, CO2 reduction, dye-sensitized and organic solar cells, and photosensitizers in photovoltaic devices) and energy storage (batteries, fuel cells, and supercapacitors). The vast coverage of advancements in environmental applications of GR-based materials for photocatalytic degradation of organic pollutants, gas sensing, and removal of heavy-metal ions is presented. Additionally, the use of graphene composites in the biosensing field is discussed. We conclude the review with remarks on the challenges, prospects, and further development of GR-based materials in the exciting fields of energy, environment, and bioscience.
Pyrolysis oil from oil palm biomass can be a sustainable alternative to fossil fuels and the precursor for synthesizing petrochemical products due to its carbon-neutral properties and low sulfur and nitrogen content. This work investigated the effect of applying mesoporous acidic catalysts, Ni-Mo/TiO2 and Ni/Al2O3, in a catalytic co-pyrolysis of oil palm trunk (OPT) and polypropylene (PP) from 500 to 700 °C. The obtained oil yields varied between 12.67 and 19.50 wt.% and 12.33-17.17 wt.% for Ni-Mo/TiO2 and Ni/Al2O3, respectively. The hydrocarbon content in oil significantly increased up to 54.07-58.18% and 37.28-68.77% after adding Ni-Mo/TiO2 and Ni/Al2O3, respectively. The phenolic compounds content was substantially reduced to 8.46-20.16% for Ni-Mo/TiO2 and 2.93-14.56% for Ni/Al2O3. Minor reduction in oxygenated compounds was noticed from catalytic co-pyrolysis, though the parametric effects of temperature and catalyst type remain unclear. The enhanced deoxygenation and cracking of phenolic and oxygenated compounds and the PP decomposition resulted in increased hydrocarbon production in oil during catalytic co-pyrolysis. Catalyst addition also promoted the isomerization and oligomerization reactions, enhancing the formation of cyclic relative to aliphatic hydrocarbon.
In this study, solid coconut waste and CaO/PVA was used as raw material and catalyst respectively to produce biodiesel through in situ transesterification. Both, raw material and catalyst were packed in a packed bed reactor. The reaction was fixed for 3 h and the mixing was kept constant at 350 rpm. The highest biodiesel yield of 95% was obtained at reaction temperature of 61 °C with catalyst loading (CaO/PVA) of 2.29 wt% and methanol to solid ratio of 12:1. CaO-waste derived catalyst has been successfully proven to be utilized as heterogeneous base catalyst for the production of biodiesel from solid coconut waste.
In this study, a novel continuous reactor has been developed to produce high quality methyl esters (biodiesel) from palm oil. A microporous TiO2/Al2O3 membrane was packed with potassium hydroxide catalyst supported on palm shell activated carbon. The central composite design (CCD) of response surface methodology (RSM) was employed to investigate the effects of reaction temperature, catalyst amount and cross flow circulation velocity on the production of biodiesel in the packed bed membrane reactor. The highest conversion of palm oil to biodiesel in the reactor was obtained at 70 °C employing 157.04 g catalyst per unit volume of the reactor and 0.21 cm/s cross flow circulation velocity. The physical and chemical properties of the produced biodiesel were determined and compared with the standard specifications. High quality palm oil biodiesel was produced by combination of heterogeneous alkali transesterification and separation processes in the packed bed membrane reactor.
The palladium metal catalysed Heck reaction of 4-iodoanisole with styrene or methyl acrylate has been studied in a continuous plug flow reactor (PFR) using supercritical carbon dioxide (scCO2) as the solvent, with THF and methanol as modifiers. The catalyst was 2% palladium on silica and the base was diisopropylethylamine due to its solubility in the reaction solvent. No phosphine co-catalysts were used so the work-up procedure was simplified and the green credentials of the reaction were enhanced. The reactions were studied as a function of temperature, pressure and flow rate and in the case of the reaction with styrene compared against a standard, stirred autoclave reaction. Conversion was determined and, in the case of the reaction with styrene, the isomeric product distribution was monitored by GC. In the case of the reaction with methyl acrylate the reactor was scaled from a 1.0 mm to 3.9 mm internal diameter and the conversion and turnover frequency determined. The results show that the Heck reaction can be effectively performed in scCO2 under continuous flow conditions with a palladium metal, phosphine-free catalyst, but care must be taken when selecting the reaction temperature in order to ensure the appropriate isomer distribution is achieved. Higher reaction temperatures were found to enhance formation of the branched terminal alkene isomer as opposed to the linear trans-isomer.
This study involves the investigation of altering the photocatalytic activity of TiO2 using composite materials. Three different forms of modified TiO2, namely, TiO2/activated carbon (AC), TiO2/carbon (C), and TiO2/PANi, were compared. The TiO2/carbon composite was obtained by pyrolysis of TiO2/PANi prepared by in situ polymerization method, while the TiO2/activated carbon (TiO2/AC) was obtained after treating TiO2/carbon with 1.0 M KOH solution, followed by calcination at a temperature of 450°C. X-ray powder diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR), thermogravimetric analysis (TG-DTA), Brunauer-Emmet-Teller (BET), and UV-Vis spectroscopy were used to characterize and evaluate the prepared samples. The specific surface area was determined to be in the following order: TiO2/AC > TiO2/C > TiO2/PANi > TiO2 (179 > 134 > 54 > 9 m(2) g(-1)). The evaluation of photocatalytic performance for the degradation of methylene blue under UV light irradiation was also of the same order, with 98 > 84.7 > 69% conversion rate, which is likely to be attributed to the porosity and synergistic effect in the prepared samples.
The optical properties of a ZnO photocatalyst were enhanced with various dopant concentrations of Fe(3+). Doped ZnO nanoparticles were synthesized via a sol-gel method without the use of capping agents or surfactants and was then characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and ultraviolet-visible (UV-Vis) spectroscopy. The results showed that ZnO has a wurtzite, hexagonal structure and that the Fe(3+) ions were well incorporated into the ZnO crystal lattice. As the Fe(3+) concentration increased from 0.25 wt.% to 1 wt.%, the crystal size decreased in comparison with the undoped ZnO. The spectral absorption shifts of the visible light region (red shift) and the band gap decreases for each Fe-ZnO sample were investigated. The photocatalytic activities of the ZnO and Fe-ZnO samples were evaluated based on the degradation of 2-chlorophenol in aqueous solution under solar radiation. The samples with a small concentration of Fe(3+) ions showed enhanced photocatalytic activity with an optimal maximum performance at 0.5 wt.%. The results indicated that toxicity removal of 2-chlorophenol at same line of degradation efficiency. Small crystallite size and low band gap were attributed to high activities of Fe-ZnO samples under various concentrations of Fe(3+) ions compared to undoped ZnO.
In this work, sand/zinc oxide (ZnO)/titanium dioxide (TiO2)-based photocatalysts were hybridized with graphene oxide (GO) and GO_multi-walled carbon nanotubes (MWCNTs) hybrid solution. The novel hybrid was then used in photocatalysis to degrade dye contamination. The nanocomposite photocatalyst was initially fabricated by growing ZnO nanorods (NRs) via sol-gel immersion followed by synthesizing TiO2 NRs for different times (5 and 20 h) using a hydrothermal method on sand as a substrate. Prior to the hybridization, the initial GO was synthesized using electrochemical exfoliation and further mixed with 1 wt% MWCNTs to form GO_MWCNTs hybrid solution. The synthesized GO and GO_MWCNTs hybrid solution were then incorporated onto sand/ZnO/TiO2 nanocomposite-based photocatalysts through immersion. Various sand/ZnO/TiO2-based photocatalysts were then tested for methylene blue (MB) dye degradation within 3 days. On the basis of UV-Vis measurement, the highest MB degradation was achieved by using sand/ZnO NRs/TiO2 NRs (5 h)/GO_MWCNTs (92.60%). The high surface area and high electrical conductivity of GO_MWCNTs prolonged the lifetime of electron/hole separation and thus enhanced the photocatalytic performance.
Lanthanide element in the methanation reaction gives an excellent catalytic performance at low reaction temperature. Praseodymium is one of lanthanide element and was chosen due to its properties which are thermally stable and provide excess of oxygen in the oxide lattice. Therefore, a catalyst of Ru/Mn/Pr (5:30:65)/Al2O3 (RMP, 5:30:65/Al2O3) was prepared via wetness impregnation method and the effect of calcination temperature on the catalyst performance was investigated using FTIR analysis. The RMP/Al2O3 catalyst calcined at 800 o C was chosen as an excel catalyst with CO2 conversion of 96.9% and CH4 formation of 45.1% at 350 o C reaction temperature. From the EDX mapping, it can be observed that the distribution of all element is homogeneous at 800 o C and 900 o C except Ru, O and Al at 1000 o C calcination temperature. The image from FESEM also shows the presence of some crystal shape on the catalyst surface. From the FTIR analysis, the peak stretching and bending mode of O-H bond decreased when the calcination temperature increased.
Liquid natural rubber (LNR) was functionalized into liquid epoxidized natural rubber (LENR) and hydroxylated LNR (LNROH)
via oxidation using a Na2
WO4
/CH3
COOH/H2
O2
catalytic system. Microstructures of LNR and functionalized LNRs
were characterized using Fourier Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopies. The
effect of CH3
COOH, H2
O2
, Na2
WO4
, reaction time and temperature. reaction time and temperature on epoxy content were
investigated. LNR-OH was obtained when oxidation reaction was conducted at a longer reaction time, higher temperature
or excess amount of catalyst. Thermogravimetric analysis (TGA) reported the thermal behavior of functionalized LNRs.
Molecular weight and polydispersity index (PDI) were determined using gel permeation chromatography (GPC).
Photocatalysis is an ecofriendly technique that emerged as a promising alternative for the degradation of many organic pollutants. The weaknesses of the present photocatalytic system which limit their industrial applications include low-usage of visible light, fast charge recombination, and low migration ability of the photo-generated electrons and holes. Therefore, various elements such as noble metals and transition metals as well as non-metals and metalloids (i.e., graphene, carbon nanotube, and carbon quantum dots) are doped into the photocatalyst as co-catalysts to enhance the photodegradation performance. The incorporation of the co-catalyst which alters the photocatalytic mechanism was discussed in detail. The application of photocatalysts in treating persistent organic pollutants such as pesticide, pharmaceutical compounds, oil and grease and textile in real wastewater was also discussed. Besides, a few photocatalytic reactors in pilot scale had been designed for the effort of commercializing the system. In addition, hybrid photocatalytic system integrating with membrane filtration together with their membrane fabrication methods had also been reviewed. This review outlined various types of heterogeneous photocatalysts, mechanism, synthesis methods of biomass supported photocatalyst, photocatalytic degradation of organic substances in real wastewater, and photocatalytic reactor designs and their operating parameters as well as the latest development of photocatalyst incorporated membrane.
Novel Sm doped Cr2O3 decorated MWCNTs nanocomposite photocatalyst was successfully prepared by a facile hydrothermal method for metoprolol (MET) degradation. A heterogeneous photo -Fenton like system was formed with the addition of H2O2 for ultrasonic irradiation (US), visible light irradiation (Vis) and dual irradiation (US/Vis) systems. The intrinsic characteristics of Sm doped Cr2O3 decorated MWCNTs nanocomposite was comprehensively performed using state-of-art characterization tools. Optical studies confirmed that Sm doping shifted the absorbance of Cr2O3 towards the visible-light region, further enhanced by MWCNTs incorporation. In this study, degradation of metoprolol (MET) was investigated in the presence of Cr2O3 nanoparticles, Sm doped Cr2O3 and Sm doped Cr2O3 decorated MWCNTs nanocomposites using sonocatalysis and photocatalysis and simultaneously. Several different experimental parameters, including irradiation time, H2O2 concentration, catalyst amount, initial concentration, and pH value, were optimized. The remarkably enhanced sonophotocatalytic activity of Sm doped Cr2O3 decorated MWCNTs could be attributed to the more formation of reactive radicals and the excellent electronical property of Sm doping and MWCNTs. The rate constant of degradation using sonophotocatalytic system was even higher than the sum of rates of individual systems due to its synergistic performance based on the kinetic data. A plausible mechanism for the degradation of MET over Sm-Cr2O3/MWCNTs is also demonstrated by using active species scavenger studies and EPR spectroscopy. Our findings imply that (•OH), (h+) and (•O2-) were the reactive species responsible for the degradation of MET based on the special three-way Fenton-like mechanism and the dissociation of H2O2. The durability and stability of the nanocomposite were also performed, and the obtained results revealed that the catalysts can endure the harsh sonophotocatalytic conditions even after fifth cycles. Mineralization experiments using the optimized parameters were evaluated as well. The kinetics and the reaction mechanism with the possible reasons for the synergistic effect were presented. Identification of degraded intermediates also investigated.
The present study defines a novel green method for the synthesis of the nickel oxide nanocatalyst by using an aqueous latex extract of the Ficus elastic. The catalyst was examined for the conversion of novel Brachychiton populneus seed oil (BPSO) into biodiesel. The Brachychiton populneus seeds have a higher oil content (41 wt%) and free fatty acid value (3.8 mg KOH/g). The synthesised green nanocatalyst was examined by the Fourier transform infrared (FT-IR) spectroscopy, energy dispersive X-Ray (EDX) spectroscopy, X-Ray diffraction (XRD) spectroscopy and scanning electron microscopy (SEM). The obtained results show that the synthesised green nanocatalyst was 22-26 nm in diameter and spherical-cubic in shape with a higher rate of catalytic efficiency. It was utilised further for the conversion of BPSO into biofuel. Due to the high free fatty acid value, the biodiesel was synthesised by the two-step process, i.e., pretreatment of the BPSO by means of acid esterification and then followed by the transesterification reaction. The acidic catalyst (H2SO4) was used for the pretreatment of BPSO. The optimum condition for the transesterification of the pretreated BPSO was 1:9 of oil-methanol molar ratio, 2.5 wt % of prepared nanocatalyst concentration and 85 °C of reaction temperature corresponding to the highest biodiesel yield of 97.5 wt%. The synthesised biodiesel was analysed by the FT-IR and GC-MS technique to determine the chemical composition of fatty acid methyl esters. Fuel properties of Brachychiton populneus seed oil biodiesel (BPSOB) were also examined, compared, and it falls in the prescribed range of ASTM standards.