Activity of solid catalysts for biodiesel production: A review

Heterogeneous catalysts are promising for the transesterification reaction of vegetable oils to produce biodiesel. Unlike homogeneous, heterogeneous catalysts are environmentally benign and could be operated in continuous processes. Moreover they can be reused and regenerated. However a high molar ratio of alcohol to oil, large amount of catalyst and high temperature and pressure are required when utilizing heterogeneous catalyst to produce biodiesel. In this paper, the catalytic activity of several solid base and acid catalysts, particularly metal oxides and supported metal oxides, was reviewed. Solid acid catalysts were able to do transesterification and esterification reactions simultaneously and convert oils with high amount of FFA (Free Fatty Acids). However, the reaction rate in the presence of solid base catalysts was faster. The catalyst efficiency depended on several factors such as specific surface area, pore size, pore volume and active site concentration.     

The production of biodiesel from vegetable oils by ethanolysis: Current state and perspectives

At present, the homogeneous base-catalyzed methanolysis reaction of vegetable oils is a most often used process for the industrial biodiesel production. The toxicity of methanol, the risk of the methanol vapor explosion and the possibility of the ethanol production from biorenewable resources have contributed to the development of a vegetable oil ethanolysis process for the biodiesel production. In the reaction of vegetable oils and ethanol in the presence of a catalyst, completely agricultural fuels consisted of fatty acid ethyl esters (FAEE) are obtained having physico-chemical properties similar to those of the appropriate methyl esters and diesel fuel. The ethanolysis reaction of various oily feedstocks has been widely studied to optimize the reaction conditions and to develop new catalytic systems and processes based on chemical and biological catalysts, as well as the development of non-catalytic processes. Most researches investigate the application of homogeneous base catalysts. This paper studies the review of vegetable oil ethanolysis investigations for the biodiesel production done so far. The goals of the paper are to present the development of FAEE synthesis by catalytic and non-catalytic processes, their advantages and disadvantages, the influence of some operating and reaction conditions on the process rate and ethyl esters yield, the kinetics models describing the ethanolysis process rate, the process optimization and the possibilities for improving the FAEE synthesis process.     

生物柴油合成催化剂的研究进展

生物柴油是典型的"绿色能源",是优质的石油柴油代用品。综述了酯交换方法生产生物柴油过程中催化剂的研究进展,并重点介绍了固体碱催化剂的研究状况。     

Growth characteristics of hierarchical ZnO structures prepared by one-step aqueous chemical growth

By varying the initial precursor concentrations of (KOH/Zn(NO₃)₂ 6H₂O) without addition of surfactants, the branched nanostructures with different growth characteristics can be obtained. In this study, the growth behavior of the three-dimensional hierarchical structure arrays varied from randomly oriented to well-defined sixfold symmetry by altering pH value of the solution and the related effect of erosion phenomenon have been illustrated. In summary, the hierarchical structures with different morphologies can be obtained on preformed Zn microtips through a simple one-step solution method.     

Fe3O4 nanoparticles impregnated eggshell as a novel catalyst for enhanced biodiesel production

Biodiesel is a green fuel which can replace diesel while addressing various issues such as scarcity of hydrocarbon fuels and environmental pollution to an extent. The high production cost of biodiesel and the recovery of the catalyst after the transesterification process are the major challenges to be addressed in biodiesel production. In the present work, a cheap and promising solid base oxide catalyst was synthesized from chicken eggshell by calcination at 900 °C forming catalyst eggshells (CES) and was impregnated with the nanomagnetic material (Fe₃O₄) to obtain Fe₃O₄ loaded catalytic eggshell (CES–Fe₃O₄). Fe₃O₄ nanomaterials were synthesized by co-precipitation method and were loaded in catalytic eggshell by sonication, for better recovery of the catalyst after transesterification process. CES–Fe₃O₄ material was characterized by Thermogravimetric analysis, X-ray diffraction, Fourier transform infrared spectroscopy, a vibrating-sample magnetometer, Brunauer-Emmett-Teller, Dynamic light scattering, and Scanning electron microscopy. Biodiesel was synthesized by transesterification of Pongamia pinnata raw oil with 1:12 oil to methanol molar ratio and 2 wt% catalyst loading for 2 h at a temperature of 65 °C and yields were compared. The reusability of the catalyst was studied by the transesterification of the raw oil and its catalytic activity was found to be retained up to 7 cycles with a yield of 98%.     

Polymeric ionic liquids (PILs) with high acid density:Tunable catalytic performance for biodiesel production

A series of polymeric ionic liquids (PILs) used as effective heterogeneous catalysts for biodiesel produc-tion via esterification of free fatty acids (FFAs) were effectively prepared by the reaction of poly (ethylene imine) (PEI) polymers with different molecular weight and 1,3-propanesultone,followed by the further acidification with differential effective acids,i.e.H2SO4,CF3SO3H,CH3SO3H or p-toluenesulfonic acid(p-TSA).Ultrahigh acidity and catalytic performance were achieved and could be fine-tuned by simply adjusting the molecular weight of PEI and by further treatment of acids.Specifically,under the optimal conditions (i.e.reaction temperature was 70 ℃,reaction time was 2.0 h,catalyst dosage was 3.15％(mass),and alcohol/acid molar ratio was 14∶1) acquired through the Box-BEHNKEN response surface methodology,a high oleic acid conversion of 98.42％ could be obtained over the optimal PIL,PEI(70000)-PS-p-TSA.Additionally,our PILs also showed high generality for esterification of other FFAs,with general high conversion over 90％ noted in each case even under much milder reaction conditions com-pared to other conventional catalysts.     

Techno-economic study of different alternatives for biodiesel production

Biodiesel has become an attractive diesel fuel substitute due to its environmental benefits since it can be made from renewable resource. However, the high costs surrounding biodiesel production remains the main problem in making it competitive in the fuel market either as a blend or as a neat fuel. More than 80% of the production cost is associated with the feedstock itself and consequently, efforts are focused on developing technologies capable of using lower-cost feedstocks, such as recycled cooking oils and wastes from animal or vegetable oil processing operations.     

Solid oxide derived from waste shells of Turbonilla striatula as a renewable catalyst for biodiesel production

Biodiesel production via transesterification of mustard oil with methanol using solid oxide catalyst derived from waste shell of Turbonilla striatula was investigated. The shells were calcined at different temperatures for 4 h and catalyst characterizations were carried out by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), Fourier transform infrared spectrometer (FT-IR), thermogravimetric analysis (TGA)/differential scanning calorimetry (DSC) and Brunauer-Emmett-Teller (BET) surface area measurements . Formation of solid oxide i.e. CaO was confirmed at calcination temperature of 800 °C. The effect of the molar ratio of methanol to oil, the reaction temperature, catalyst calcination temperature and catalyst amount used for transesterification were studied to optimize the reaction conditions. Biodiesel yield of 93.3% was achieved when transesterification was carried out at 65 ± 5 °C by employing 3.0 wt.% catalyst and 9:1 methanol to oil molar ratio. BET surface area indicated that the shells calcined in the temperature range of 700 °C-900 °C exhibited enhanced surface area and higher pore volume than the shells calcined at 600 °C. Reusability of the catalysts prepared in different temperatures was also investigated.     

Kalsilite based heterogeneous catalyst for biodiesel production

Kalsilite (KAlSiO₄) was used as a heterogeneous catalyst for transesterification of soybean oil with methanol to biodiesel. Kalsilite showed relatively low catalytic activity for transesterification reaction. The catalytic activity of this catalyst was significantly enhanced by introducing a small amount of lithium nitrate by the impregnation method. A biodiesel yield of 100% and a kinematic viscosity of 3.84 cSt were achieved at a mild temperature of only 120 °C over this lithium modified kalsilite catalyst (2.3 wt.% Li).     

Advancements in development and characterization of biodiesel: A review

An ever increasing demand of fuels has been a challenge for today’s scientific workers. The fossil fuel resources are dwindling day by day. Biodiesel seems to be a solution for future. Biodiesel is an environmentally viable fuel. Out of the four ways viz. direct use and blending, micro-emulsions, thermal cracking and transesterification, most commonly used method is transesterification of vegetable oils, fats, waste oils, etc. Latest aspects of development of biodiesel have been discussed in this work. Yield of biodiesel is affected by molar ratio, moisture and water content, reaction temperature, stirring, specific gravity, etc. Biodegradability, kinetics involved in the process of biodiesel production, and its stability have been critically reviewed. Emissions and performance of biodiesel has also been reported.     

Life cycle analysis of biodiesel production

Biodiesel has attracted considerable attention as a renewable, biodegradable, and nontoxic fuel and can contribute to solving the energy problems, significantly reducing the emission of gases which cause global warming.The first stage of this work was to simulate different alternative processes for producing biodiesel. The method used for the production of biodiesel is the transesterification of vegetable oils with an alcohol in the presence of a catalyst. The raw materials used were palm oils and waste cooking oil.The second stage was a life cycle analysis for all alternatives under study, followed by an economic analysis for the alternatives that present minor impacts and which are more promising from an economic point of view. Finally, we proceeded to compare the different alternatives from both the point of view of life cycle and economic analysis.The feasibility of all processes was proven and the biodiesel obtained had good specifications.From the standpoint of life cycle analysis, the best alternative was the process of alkaline catalysis with acid pre-treatment for waste cooking oil.The economic analysis was done to the previous mentioned process and to the process that uses raw virgin oils, methanol, and sodium hydroxide. This process has lower investment costs but the process of alkaline catalysis with acid pre-treatment, whose main raw material is waste oil, is much more profitable and has less environmental impacts.     

One step from nanofiber to functional hybrid structure: Pd doped ZnO/SnO2 heterojunction nanofibers with hexagonal ZnO columns for enhanced low-temperature hydrogen gas sensing

In this paper, a novel hybrid structure of Pd doped ZnO/SnO₂ heterojunction nanofibers with hexagonal ZnO columns was one step synthesized from electrospun precursor nanofibers. Due to the synergistic effect of hexagonal ZnO, SnO₂ and Pd, the structure exhibited excellent hydrogen (H₂) gas sensing properties. At low-temperature of 120 °C, the response (R_a/R_g) to 100 ppm H₂ gas exceeded 160, the response/recovery time was only 20 s and 6 s respectively and the limit of detection was only 0.5 ppm. Meanwhile, it also had good selectivity for H₂ gas and excellent linearity. In addition, the materials were characterized by XRD, FESEM, HRTEM, XPS, and the synthesis mechanism and gas sensing mechanism were proposed.     

Controllable growth of ZnO nanorod arrays with different densities and their photo-electric properties

ABSTRACT: Since the photo-electric response and charge carriers transport can be influenced greatly by the density and spacing of the ZnO nanorod arrays, controlling of these geometric parameters precisely is highly desirable but rather challenging in practice. Here, we fabricated patterned ZnO nanorod arrays with different density and spacing distance on silicon (Si) substrate by electron beam lithography (EBL) method combined with the subsequent hydrothermal reaction process. By using the EBL method, patterned ZnO seed layers with different areas and spacing distances were obtained firstly. ZnO nanorod arrays with different density and various morphologies were obtained by the subsequent hydrothermal growth process. The combination of EBL and hydrothermal growth process was very attractive and made us could control the geometric parameters of ZnO nanorod arrays expediently. Finally, the vertical transport properties of the patterned ZnO nanorod arrays were investigated through the micro probe station equipment and the I-V measurement results indicated that back-to-back Schottky contacts with different barriers height were formed in dark conditions. Under UV light illumination, the patterned ZnO nanorod arrays showed a high UV light sensitivity, and the response ratio was about 104. The controllable fabrication of patterned ZnO nanorod arrays and understanding for their photo-electric transport properties were helpful to improve the performance of nanodevices based on them.     

One-step solution synthesis of urchin-like ZnO superstructures from ZnO rods

The urchin-like ZnO superstructures have been directly prepared by the assistance of poly (acrylic acid) (PAA, M_w 5000) under a one-step solution-based process. X-ray diffraction (XRD) patterns indicate that the crystal structure of the special ZnO urchins is hexagonal. The results of Field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) tests show that the urchins are composed of rods and the average aspect ratio of them is about 10 with a length of about 1.5 μm. Selected area electron diffraction (SAED) pattern reveals that the rods are single crystal in nature, which preferentially grow up along the 〈0001〉 direction. Furthermore, the sizes and aspect ratios of the rods can be easily controlled by regulating the concentration of ZnSO₄ solution. It is believed that the process of crystallization, including nucleation and crystal growth, happens along PAA chains resulting in the production of rods and assembly of them into superstructures.     

Application of KF/MgO as a heterogeneous catalyst in the production of biodiesel from rapeseed oil

Biodiesel was synthesized from rapeseed oil by transesterification over Magnesium oxide loaded with KF. The catalytic activity strongly depends on the loading amount of KF and calcined temperature. We found that the reaction reached a 79.37% yield when the loading amount was at 35 wt% and calcined at 500 °C. The simply dried 30% KF/MgO at 80 °C was found to give equally good results from the catalyst calcined at 500 °C, avoiding the usual activation at high temperature. The catalysts were characterized by the Hammett indicator method, BET, TG/DTG, XRD, NMR, EDS, and FT-IR. According to the instrumental analysis, the activity in the transesterification probably belonged to coordinately unsaturated F⁻ and liberation of hydroxide during preparation. The effects of methanol/oil ratio and catalyst amounts on the conversion were also studied in this paper.     

Model-based optimisation of biodiesel production from microalgae

This work presents a superstructure-based optimisation model to optimise the microalgae to biodiesel production flowsheet for the minimum net annualised life cycle cost (ALCC) of biodiesel. The model includes the important processing steps of converting microalgae into biodiesel, viz. microalgae growth, harvesting, lipid extraction, and transesterification of lipid. Different options to perform these steps are considered. The mass and volumetric balance for each process and equipment, and the equipment capacity limitations constitute the important model constraints. The decision variables include growth duration, medium, as well as the techniques and specifications to be followed in each of the downstream steps. The mixed integer linear programming model was applied to a case study of producing 30,000 kg/d biodiesel from Chlorella. The minimum ALCC was US $ 13.286/l for the flowsheet and equipment details recommended by the model. Sensitivity analysis showed that lipid extraction was the most crucial step in the flowsheet.     

Enhanced photocatalytic performance of ZnO/multi-walled carbon nanotube nanocomposites for dye degradation

The ZnO nanowire/multi-walled carbon nanotube (MWNT) nanocomposites have been successfully synthesized by one-step hydrothermal method using zinc chloride as Zn source. Their photocatalytic degradation performances on methylene blue and Rhodamine 6G have been investigated under UV irradiation. Experimental results show that the photocatalytic efficiency of the as-synthesized ZnO/MWNT nanocomposites is 3 times higher than that of pure ZnO nanowires. The enhanced photocatalytic activity is attributed to the fast transfer of photo-generated electrons from ZnO to MWNTs, leading to low recombination rate of photo-induced electron–hole pairs.     

Long term activity of modified ZnO nanoparticles for transesterification

Biodiesel can be produced by the transesterification of natural oils with methanol using modified ZnO nanoparticles as catalyst. Crude algae oil, corn oil from DDGs, crude palm oil, crude soybean oil, crude coconut oil, waste cooking oil, food-grade soybean oil and food-grade soybean oil with 3% water and 5% FFA addition were converted into FAME within 3 h using this new catalyst. The ZnO nanoparticles were reused 17 times without any activity loss in a batch stirred reactor and the average yield of FAME was around 93.7%. ZnO nanoparticles were used continuously for 70 days in a fix bed continuous reactor and the average yield of FAME was around 92.3%. XRD, ICP, TEM and HRTEM were used to characterize the long term used catalyst structure. Results show that this catalyst is a mixture of wurtzite ZnO nanoparticles and some amorphous materials and that the used catalysts have similar crystal structure to fresh catalyst. ICP results show that this catalyst does not dissolve in biodiesel, methanol, oil and glycerine-methanol solutions. It has a stable crystal structure under the reaction conditions. The high catalytic activity, long catalyst life and low leaching properties demonstrate these modified ZnO nanoparticles have potential in a commercial biodiesel production process.     

Optimization of the transesterification reaction in biodiesel production

In this paper response surface methodology (RSM) was used to study the transesterification reaction of rapeseed oil for biodiesel production. The three main factors that drive the conversion of triglycerides into fatty acid methyl esters (FAME) were studied according to a full factorial design at two levels. These factors were catalyst concentration (KOH), temperature and reaction time. The range investigated for each factor was selected taking into account the process of Fox Petroli S.p.A. Analysis of variance (ANOVA) was used to determine the significance of the factors and their interactions which primarily affect the first of the two transesterification stages. This analysis evidenced the best operating conditions of the first transesterification reaction performed at Fox’s plant: KOH concentration 0.6% w/w, temperature 50 °C and reaction time 90 min with a CH₃OH to KOH ratio equal to 60. Three empirical models were derived to correlate the experimental results, suitable to predict the behavior of triglyceride, diglyceride and monoglyceride concentration. These models showed a good agreement with the experimental results, demonstrating that this methodology may be useful for industrial process optimization.     

Optical properties of group-I-doped ZnO nanowires

Undoped and group-I elements doped ZnO nanowires were synthesized using a thermal evaporation method. Field emission scanning electron microscopy (FESEM) results showed that, the undoped ZnO nanowires were ultra-long with uniform diameters. On the other hand, the length of the doped ZnO nanowires was in the range of some hundred of nanometers. X-ray diffraction (XRD) patterns clearly indicated hexagonal structures for all of the products. X-ray photoelectron spectroscopy (XPS) studies confirmed the oxidation states of Li, Na, K, in the ZnO lattice. An asymmetric O 1s peak indicated the presence of oxygen in an oxide layer. The effect of doping on the optical band-gap and crystalline quality was also investigated using photoluminescence (PL), UV–vis, and Raman spectrometers. The Raman spectra of the products indicated a strong E₂ (high) peak. The PL spectra exhibited a strong peak in the ultraviolet (UV) region of the electromagnetic spectrum for all of the ZnO nanowires. The UV peak of the doped ZnO nanowires was red-shifted compared to the undoped ZnO nanowires. In addition, the UV–vis spectra of the samples showed similar results compared to the PL results.