Calcium Oxide Catalyst Research Articles

Biodiesel production from cotton oil using heterogeneous CaO catalysts from eggshells prepared at different calcination temperatures

Abstract Biodiesel is a fuel from vegetable oil or animal fat, and is a promising substitute for petroleum-derived diesel. Transesterification is the most widely used method in biodiesel production. Eggshell is rich in calcium carbonate (CaCO3), and when it is subjected to heat treatment it results in calcium oxide (CaO). CaO from eggshells was prepared at different calcination temperatures, and characterized by X-ray diffraction, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The obtained CaO was used as a catalyst. All catalysts showed good stability and excellent morphology for biodiesel synthesis. Catalytic activity was evaluated by the methyl transesterification reaction of cotton oil for 3 h, 9:1 methanol:oil molar ratio, 3 wt% (catalyst/oil weight ratio) catalyst and 60°C. Biodiesels showed an ester content of 97.83%, 97.23% and 98.08%, obtained from calcined eggshell at 800°C, 900°C and 1000°C, respectively. Biodiesel quality was affected by the acidity of the cation exchange resin. The kinematic viscosity of biodiesel was in accordance with specification, except for the biodiesel obtained from the calcined catalyst at 1000°C. The CaO from eggshells obtained at different calcination temperatures is promising for biodiesel synthesis.

Production of Karanja Methyl Ester from Crude Karanja Oil Using Meretrix Lyrata Synthesised Active CaO Catalyst

Active calcium oxide catalyst was synthesised from Meretrix Lyrata (M.Lyrata) following calcination-hydration-dehydration technique. The catalytic feasibility of synthesised CaO was investigated in the production of Karanja methyl ester (KME) from crude Karanja oil (CKO). KME was synthesised through esterification using followed by transesterification utilising CaO in a two-step reaction process of CKO and methanol. The M.Lyrata shells were calcined at 900 ℃ and the catalyst samples were characterised using FTIR, SEM, PSA, and BET-BJH spectrographic techniques. A maximum fatty acid methyl ester (FAME) conversion of 97.3 % was obtained at optimum reaction conditions including methanol-to-oil ratio of 12:1, catalyst concentration of 2 wt.%, reaction temperature of 58 ℃ and reaction time of 2 hrs. In a comparative study with commercial CaO, M.Lyrata showed a higher catalytic activity. The catalyst reusability experiments ascertaining reusability of CaO up to four reuse cycles had shown good efficiency. The economic comparative study confirms that CaO derived from M.Lyrata can be used as an alternative and feasible catalyst for biodiesel production. The KME fuel properties complied to EN-14214 biodiesel fuel standards.

Performance comparison of different cavitation reactors for biodiesel production via transesterification of palm oil

This study compares performance of different cavitation reactors for biodiesel production from palm oil using homogeneous and heterogeneous reaction systems. In addition, the effect of reaction volume of each reactor type was also investigated. For the smallest reaction volume of 165 mL, homogenizer and 20 kHz ultrasonic reactors offered the highest fatty acid methyl ester yield for both sodium hydroxide and calcium oxide catalysts. When the reaction volume was increased from 165 to 500 and 1000 mL with constant power input (80 W), homogenizer reactor did not significantly alter the rate of fatty acid methyl ester formation, unlike the other reactors which showed the decrease in the reaction rate. The reactor performance was evaluated in term of yield efficiency which was based on the amount of fatty acid methyl ester production, power consumption and reaction time. The increase of the reaction volume increased the yield efficiency of both the cavitation reactors and the mechanical stirred reactor. The highest yield efficiencies of 169.46 × 10−4 and 8.27 × 10−4 g/J were obtained from homogenizer reactor using sodium hydroxide and calcium oxide catalysts, respectively, using the reaction volume of 1000 mL. The homogenizer reactor also shows high flexibility of reaction volume usage with high biodiesel production performance in a batch system.

Efficacy of newly developed nano-crystalline calcium oxide catalyst for biodiesel production

The present work proposes the synthesis of nanocrystalline calcium oxide by sonication assisted reverse emulsion technique. The synthesized and the commercially available calcium oxide were characterized by various techniques. The prepared material possesses 1.53 times higher specific surface area as compared to commercial calcium oxide due its smaller crystallite size and particle size. The performance of both the calcium oxide as a catalyst were investigated for the transesterification reaction of soybean oil under ultrasound irradiation with identical reaction conditions of power and frequency. The influence of different operating parameters on the conversion of soybean oil were studied for the synthesized catalyst. Under the optimal operating conditions viz. nanocrystalline catalyst loading of 4 wt% of oil, methanol to oil molar ratio of 6:1, temperature of 60 °C and ultrasonic power of 212.89 kW/m2, the conversion of oil was 89.89% in 80 min of reaction time. The synthesized catalyst shows 18.81% enhanced conversion of oil as compared to commercial catalyst at the same operating conditions. Finally, the activation energy of reaction was also determined at the optimized operating conditions for the synthesized catalyst and was found to be 54.26 kJ/mol.

Statistical optimization of biodiesel production from Prunus armeniaca oil over strontium functionalized calcium oxide

Rapid industrialisation and hike in fuel prices has led to a growing concern for the development of alternative fuel from renewable sources. Biodiesel is one of the promising biofuels as a replacement to petroleum diesel in the future. The present study reports the synthesis of a strontium functionalised calcium oxide (Sr/CaO) catalyst via wet impregnation method for biodiesel production from Prunus armeniaca oil. The characterisation data suggested the formation of fine particles of Sr/CaO catalyst with high pore diameter after the solid phase reaction. Response surface methodology in conjunction with central composite design was applied for the development of a quadratic model to optimize the biodiesel yield. The optimal yield of 90.4% was obtained at the following reaction conditions: 1.75% (w/v) catalyst dose, 12:1 methanol to oil molar ratio, 60 °C reaction temperature and 140 min reaction time and the prepared catalyst could be reused for four times with slight loss in activity. The obtained result was found to be in agreement with the predicted values which verified the accuracy of the model.

Highly active Cao catalysts from waste shells of egg, oyster and clam for biodiesel production

Calcium oxide (CaO) catalysts derived from waste shells of egg, oyster and clam were prepared and used in the methanolysis of soybean oil. Eggshells were subjected to ultrasound irradiation and mollusc shells were subjected to calcination-hydration-calcination cycles to increase the surface area of CaO and improve its catalytic activity. The catalysts were characterized by XRD, TPD-CO2, TG-DSC, DLS and N2 adsorption, while the catalytic activity for the methanolysis of soybean oil was evaluated. Five hours of sonication reduced the CaO particle size by 34%, which resulted in a 56% increase in the activity. Two cycles of hydration-dehydration applied to the material obtained by calcination of oyster shells provided CaO with 27 m2 g−1. The transesterification rate was 2.5 times higher than that obtained with the untreated sample. After treatments, highly active CaO was obtained which indicates its enormous potential for biodiesel production. A kinetic model assuming the adsorption of methoxide anions on the surface of CaO particles was proposed.

Optimization of Biodiesel Production over Chicken Eggshell-Derived CaO Catalyst in a Continuous Centrifugal Contactor Separator

Solid calcium oxide (CaO) catalyst was prepared via the calcination of chicken eggshells as an environmentally friendly waste resource and incorporated in a continuous centrifugal contactor separator (CCCS) for intensified biodiesel synthesis. Biodiesel or fatty acid methyl esters (FAME) were produced via the transesterification of sunflower oil (containing 5 wt % tetrahydrofuran as a cosolvent) with methanol under 60 °C and separated from the glycerol and catalyst phases continuously in the CCCS. The influence of reaction parameters on biodiesel production was well modeled by response surface methodology. At an oil flow rate of 9 mL/min, an alcohol to oil molar ratio of 11:1, and a weight hourly space time (defined as the catalyst weight over the oil mass flow rate) of 0.050 h, an optimized FAME yield of 83.2% with a productivity of 638 kgFAME/(m3reactor·h) was achieved. CaO catalyst was reused without significant activity loss for at least four cycles.

Optimization of Methyl Ester Production from Waste Palm Oil Using Activated Carbon Supported Calcium Oxide Catalyst

In this study, methyl ester (ME) was produced by transesterification of waste cooking palm oil (WPO) using activated carbon supported calcium oxide as a solid base catalyst (CaO/AC). Process optimization using response surface methodology (RSM) was applied to study the effect of reaction time, molar ratio of methanol to oil, reaction temperature and catalyst amount to produce highest ME content. The optimum reaction condition was at 5.5 wt% catalyst amount, 170 °C temperature, 15:1 methanol to oil molar ratio and 2 h 22 min reaction time. The predicted and experimental ME content were found to be 80.02% and 77.32%, respectively.

Continuous Production of Biodiesel from Rubber Seed Oil Using a Packed Bed Reactor with BaCl2 Impregnated CaO as Catalyst

The goal of this research was to test barium chloride (BaCl2) impregnated calcined razor clam shell as a solid catalyst for transesterification of rubber seed oil (RSO) in a packed bed reactor (PBR). The waste razor clam shells were crushed, ground, and calcined at 900 °C in a furnace for 2 h to derive calcium oxide (CaO) particles. Subsequently, the calcined shells were impregnated with BaCl2 by wet impregnation method and recalcined at 300 °C for 2 h. The synthesized catalyst was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), Brunauer-Emmett-Teller (BET) surface area, and basic strength measurements. The effects of various parameters such as residence time, reaction temperature, methanol/oil molar ratio, and catalyst bed length on the yield of fatty acid methyl ester (FAME) were determined. The BaCl2/CaO catalyst exhibited much higher catalytic activity and stability than CaO catalyst influenced by the basicity of the doped catalyst. The maximum fatty acid methyl ester yield was 98.7 % under optimum conditions (residence time 2.0 h, reaction temperature 60 °C, methanol/oil molar ratio 12:1, and catalyst bed length 200 mm). After 6 consecutive reactions without any treatment, fatty acid methyl ester yield reduced to 83.1 %. The option of using waste razor clam shell for the production of transesterification catalysts could have economic benefits to the aquaculture and food industries.

Fatty Acid Methyl Esters Production from Waste Catfish Fat (Pangasius Hypothalamus) Using Barnacle-Zno As A Catalyst

The abundance and diverse populations of Barnacle shells catching the intention as a source of calcium oxide catalyst to transesterify waste catfish fat into methyl ester. Calcium oxide supported with zinc oxide was prepared by ball milling method at 1:2 ratios, calcined for 3 h at 400 °C. The characterization of catalyst revealed both metals were well integrated into a bimetallic oxide. The optimal conditions were found to be: methanol/oil mass ratio, 10:1; catalyst amount, 11 wt% at the reaction temperature, 65 °C with 3 h of reaction time achieving 85.7% of methyl ester conversion. Both feedstock and catalyst from waste source have been successfully utilized to produce biodiesel.

Transesterification of non-edible oils over potassium acetate impregnated CaO solid base catalyst

Biodiesel production through transesterification reaction with methanol using calcium oxide (CaO) as a solid base catalyst is restricted due to the need to the high molar ratio of methanol to oil and long reaction time. Therefore, the CaO catalyst was modified by potassium acetate (PA) to prepare PA/CaO solid base catalyst via wet impregnation method. X-ray Diffraction, Scanning Electron Microscopy, Thermal Gravimetric Analysis, Fourier Transform Infra-Red spectroscopy, Hammett indicator (basic strength), and the Inductive Couple Plasma techniques, were applied to characterize the prepared catalyst. The effect of the PA ratio loaded on CaO and calcination temperature were investigated as well. The catalyst activity was tested through transesterifcation reaction of non-edible oils, namely bitter almond oil BAO and waste fish oil WFO, with methanol. Transesterifcation process was optimized through the parameters involving the solid catalyst amount, methanol to oil molar ratio, reaction temperature, and reaction time. The highest methyl ester yield from both BAO (91.22 wt%) and WFO (93.30 wt%) were achieved by employing 2.0 wt% , and 1.0 wt% of PA/CaO catalyst, respectively, 9:1 methanol to oil molar ratio, 60 °C reaction temperature, and 120 min reaction time. The prepared catalyst was retrievable and thermally stable giving a yield up to 75 wt% after a 4th cycle reuse. The fuel properties of the raw oils were significantly enhanced as a result of transesterification, and were in conformity with the ASTM D 6751 limits. Conversion of the non-edible oils to biodiesel using the catalyst was confirmed by 1H NMR spectroscopy which gives yield percent close to those of the practically obtained. Moreover, the FTIR spectroscopy assured the conversion of the non-edible oils into biodiesel. As such, PA/CaO composite may be considered as a promising solid base catalyst for transesterification of non-edible oils with methanol.

The Application of Modified Marlstones in Biofuel Technology

Nowadays, researchers have made attempts to seek for cost-effective and eco-friendly catalyst for transesterification reaction. One possible way to reduce the costs of the catalysts is to use biomass or industrial waste as catalytic materials. The use of waste materials as catalysts also reduces the cost of waste handling and disposal. The objective of this study was to investigate the potential of the low cost, environmentally friendly calcined marlstones to be a viable catalyst in the transesterification of Jatropha seed oil. The calcination of marlstones was conducted at 900 °C for 4 h, and then the modification of calcined marlstones via hydration-dehydration treatment. The effects of different preparation conditions on biodiesel yield were investigated. The solid catalyst was characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and the Brunauer-Emmett-Teller (BET) method. The highest biodiesel yield of 97.56% for modified calcium oxide (CaO) catalyst was obtained under the optimum condition (reaction time 5 min, microwave power 600 W, methanol/oil molar ratio 9:1, and catalyst dosage 7 wt%). It was showing potential applications of novel catalyst in biodiesel industry.

The Kinetics of Calcium Oxide Catalyzed Esterification of Glycerol with Free Fatty Acids Using Pseudo-homogeneous Model Approach

Abstract This research aims to study the reaction kinetics of esterification reaction of glycerol with free fatty acid (FFA) using calcium oxide catalyst to produce mono-diacylglycerol (MDAG) using pseudo-homogeneous approach. The effects of time and temperature on the reaction conversion were investigated simultaneously. The FFA used was from the waste of cocoa production process, while the solid catalyst used was calcium oxide from eggshell ash. The results show that the cocoa based FFA was composed of palmitic acid (49.24%), methyl stearate (1.05%), oleic acid (25.39%), and stearic acid (24.32%). The calcium oxide content in the eggshell ash was 60% w/w. At all temperatures studied (60, 70, and 80oC), as the reaction time increased, the conversion increased sharply in the first 5 minute followed by a gradual raise to an almost constant value after 20 minutes (0.844; 0.845; and 0.854, respectively). Pseudo-homogeneous second order model can describe the reaction kinetics satisfactorily. The reaction constants (k) at 60, 70, and 80oC were 0.00384, 0.003401, and 0.003518 (L/mole.minute), respectively. The effects of temperature on reaction rate obey the Arrhenius’ equation with collision factor (A) is 0.2659 (L/mole.minute) and activation energy (Ea) is 3544 J/mol. Keywords: calcium oxide; free fatty acid; glycerol; pseudo-homogeneous approach

CaO Nanocatalyst for Transesterification Reaction of Palm Oil to Biodiesel: Effect of Precursor’s Concentration on the Catalyst Behavior

Depletion of fossil fuel sources in a few decades due to industrialization and motorization has led to a keen interest in the production of alternative fuels like biodiesel. Research on the development and improvement of more efficient transesterification process for biodiesel production has attain great attention in the last decade. The using of low cost catalyst is one of the main focuses on the biodiesel production. As a basic heterogeneous catalyst, CaO has been examined in the transesterification of vegetable oils for biodiesel production. In this research, calcium oxide (CaO-X) catalysts were prepared by sol-gel method at different Ca2+ precursor concentration (X = 1.0, 1.5, 2.0 M). The crystalline structure and morphology of the synthesized catalysts were characterized by means of x-ray diffraction (XRD) and N2 adsorption-desorption analysis. All the synthesized catalysts were then applied to transesterification reaction of palm oil to produce biodiesel. The characterization by x-ray diffraction demonstrate CaO-1.0 was partially hydrated due to the incomplete reaction during synthesis. As a matter of fact, formation of H2O on the surface of CaO causes lower basic strength of the catalysts, thus responsible in lowering the catalytic activity. It is demonstrated that CaO-2.0 exhibits mesoporous structure with least chemisorb amount of H2O on the catalysts surface has a very active catalytic activity. It was found that 2.0M of calcium precursor has high catalytic activity and 81% FAME yield was obtained within 3h reaction.

Calcium Oxide Catalyst Based on Quail Eggshell for Biodiesel Synthesis from Waste Palm Oil

Calcium oxide decomposed from quail eggshell was used as catalyst for biodiesel synthesis from waste palm oil. Prior to being used, the quail eggshell was decomposed at 600-1100 o C to form calcium oxide and it was characterized by X-Ray measurement, FTIR and SEM spectroscopy to analyze the functional groups and the surface morphology, followed by N 2 adsorption desorption methods to determine the surface area. The results of X-Ray analysis powder pattern show that the decomposition of quail eggshell at 900 o C gave calcium oxide that has similar characteristic to the standard CaO from Joint Committee of Powder Diffraction Standard (JCPDS). The FTIR spectrum indicated vibration of calcium oxide from quail eggshell have a similar pattern with the calcium oxide of the standard. The SEM analysis showed that morphology of quail eggshell was changed after decomposition at 900 o C and it have the mesoporous structure. The biodiesel from waste palm oil was synthesized using CaO catalyst from quail eggshell decomposed at 900 o C. The biodiesel product has density of 0.86 g/cm 3 , viscosity of 5.50 mm 2 /s, free fatty acid of 0.56 mg/KOH, and iodine number of 60.49 g I 2 /100g, respectively. All those biodiesel characteristics meet to the biodiesel standard by the Indonesian National Standard (SNI).

Preparation of CaO/Fly ash as a catalyst inhibitor for transesterification process off palm oil in biodiesel production

A palm fly ash supported calcium oxide (CaO) catalyst was prepared and used in transesterification from off-grade palm oil for biodiesel production. The catalyst synthesized by loading CaO of calcium nitrate tetrahydrate (Ca(NO3)2.4H2O) into fly ash through impregnation method. The optimum catalyst preparation conditions were determined by influence of calcination temperature and weight ratio of Ca(NO3)2.4H2O and fly ash. Catalyst with highest catalytic activity was achieved when calcined at 800 °C and proportion of Ca(NO3)2.4H2O to fly ash is 80:20. Under the conditions of oil : methanol ratio of 1:6, catalyst dosage of 6 wt% and temperature of 70 °C for 2 h, the biodiesel yield reaches to 71.77%. CaO, SiO2, Ca(OH)2 and Ca2SiO4 were found in the catalyst through X-ray diffraction (XRD) while the basic strength of the catalyst H_ in the range 9.3 – 11. Surface area of the developed catalyst is 24.342 m2/g through Brunauer-Emmett-Teller (BET). Characteristics of biodiesel such as density, kinematic viscosity, acid value, flash point has been matched with standard for biodiesel specification of Indonesia.

Study of performance, combustion and emission characteristics of heterogeneous catalyzed yellow oleander biodiesel on Compression Ignition (CI) engine

ABSTRACTIn this study, yellow oleander biodiesel was produced using a calcium oxide catalyst. The fuel properties of the yellow oleander biodiesel were in the range of ASTM standards. Effects of the yellow oleander biodiesel and its blends (B10, B20, B30, B40 and B100) were investigated at five different loads (0, 25, 50, 75 and 100%) in a single-cylinder CI engine. Comprehensive combustion analysis showed that the starts of injection timings were inadvertently advanced from the system response. The combustion of yellow oleander biodiesel and its blends generally resulted in a shorter ignition delay period for all loads due to earlier combustion timing. The performance, combustion and emission characteristics of yellow oleander biodiesel and its blends were studied. Variation in the engine emissions were recorded using an AVL DIGAS 444 analyzer. The CO and HC emissions were less for biodiesel test blends (except B100) but NOx emissions increased with closer engine performance when compared to diesel.

Effect of barium loading on CaO derived from waste egg shell heterogeneous catalyst for canola oil biodiesel

The purpose of this research was to investigate the catalytic activity of Ba loading on calcium oxide (CaO) catalyst by varying the amount of barium added during the synthesis: 5-15 wt%. The waste egg shells were utilized as a CaO heterogeneous catalyst by calcined at 900 °C for 2 h. The Ba/CaO catalysts were prepared by impregnation method and were used as a catalyst in transesterification reaction of canola oil via microwave irradiation under microwave power 300 W. The characterization of catalyst and FAME composition of biodiesel were determined by X-ray fluorescence (XRF), scanning electron microscope (SEM), Fourier transform infrared spectrometer (FTIR), and gas chromatography (GC-FID). The conditions of biodiesel production were operated at 60 °C, 3 wt% of catalyst loading, 9:1 methanol-to-canola oil ratio, and microwave irradiation power was 300W for 2 min. The experimental results found that, the waste egg shells consist mainly of CaCO3, which was decomposed to CaO more than 88 wt% after cacination step. The 15 wt% Ba/CaO catalysts exhibited the best catalytic performance with the FAME conversion higher than 97.68%.

Synthesis and characterisation of rubber seed oil trans-esterified biodiesel using cement clinker catalysts

ABSTRACTThe synthesis of biodiesel using rubber seed oil by a transesterification reaction using cement clinker catalysts was studied. The mineral composition and morphology of both the catalysts were analysed using X-ray diffraction and scanning electron microscopy. The gas chromatography–mass spectrometry, Fourier transform infrared spectroscopy and nuclear magnetic resonance studies were used to find the Fatty acid methyl ester content and various compounds of esters in the synthesised biodiesel, which showed an efficient conversion of rubber seed oil to biodiesel. The highest yield of 80% was obtained from calcium oxide catalyst (1.5 g) activated at 50°C with a methanol-to-oil ratio of 6:1. The highest yield of 70% biodiesel was obtained using a cement clinker catalyst (0.5 g) activated at 50°C with a methanol-to-oil ratio of 6:1. The significant physical properties of biodiesel flash point, acid value and saponification value were found, and the results are within the American standard test method (ASTM D6751) limits.

Rice bran oil based biodiesel production using calcium oxide catalyst derived from Chicoreus brunneus shell

Environmental pollution and the declining global supply of accessible fossil fuels are the key drivers of the search for alternative sources of energy. Biodiesel, a renewable liquid transport fuel, is commercially-produced using heterogeneous catalysts. Heterogeneous catalysts obtained from seashells appeared as promising alternatives thanks to their low preparation cost and increased efficiency in transesterification. In this study, shells from Chicoreus brunneus (known as Adusta murex) were calcined, hydrated, and dehydrated to produce CaO heterogeneous nanocatalyst for the transesterification of rice bran oil into biodiesel. Field emission scanning electron microscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, surface area measurement (Brunauer-Emmett-Teller method), and X-ray diffraction were used to characterise the seashell-derived catalyst. The properties of the rice bran oil-derived biodiesel (acid value, calorific value, density, oxidation stability, and flash point) conformed to the American Society of Testing and Materials (ASTM) D6751 and European EN 14214 biodiesel standards, except for kinematic viscosity. Therefore, the impact of the parameters used for production of the CaO heterogeneous nanocatalyst (calcination temperature and time) and the transesterification reaction (catalyst loading and methanol to rice bran oil ratio) on the kinematic viscosity of RBO-derived biodiesel were determined. A model for the transesterification process was developed using a combination of artificial neural networking with ant colony optimisation. The model predicted that C. brunneus-derived CaO catalyst prepared at 1100 °C for 72 min could be used to produce biodiesel from rice bran oil with a minimum kinematic viscosity (4.42 mm2 s−1) confirming to both the ASTM D6751 and EN 14214 biodiesel standards in a transesterification reaction operating with a 35:1 methanol to rice bran oil molar ratio and 0.5 wt% catalyst mass.