CaO Catalyst Research Articles

Glycerolysis of Palm Fatty Acid Distillate (PFAD) as Biodiesel Feedstock Using Heterogeneous Catalyst

Biodiesel is normally produced through transesterification of triglycerides with methanol in the presence of an alkaline catalyst. With the uncertain crude oil prices and competition of vegetable oils used for food purposes, alternative feedstock for biodiesel production has to be studied. In this study, palm fatty acid distillate (PFAD), a by-product of the palm oil refinery was used as a feedstock. Glycerolysis reaction was carried out from 160 to 200 °C in the presence of a natural CaO catalyst derived from raw chicken eggshell. The commercial CaO was also evaluated as a control. The results showed that the free fatty acid (FFA) was reduced from 81 to 1.5% using activated eggshell as catalyst at reaction temperature of 180 °C and catalyst dosage of 1.5 wt% while commercial CaO reduced FFA to 3.7% at reaction temperature of 200 °C and 1.5 wt% of catalyst dosage, respectively. The treated PFAD can be used for biodiesel production.

Optimization processes of biodiesel production from pig and neem (Azadirachta indica a.Juss) seeds blend oil using alternative catalysts from waste biomass

This study tested the suitability of solid residue (CaO) derived from the mixture of wastes biomass as based catalyst transesterification conversion of the blend of neem oilseed (Azadirachta indica A.Juss) with rendered pig fat. Blending was done in the ratio of Neem oil: Pig fat oil (v/v) as 10:90 (NO10),20:80 (NO20),30:70 (NO30), 40:60 (NO40), 50:50 (NO50), 60:40 (NO60), 70:30 (NO70), 80:20 (NO80), and 90:10 (NO90), respectively. Process parameter transesterification optimization of methanolysis CaO catalyst for synthesis of 60:40 to mixed oil biodiesel (MOB) was investigated using central composite design that generates thirty experimental runs and were carried out.Results showed low viscous oil at blend of 60:40. The predicted MOB yield of 98.05 (wt. %) at catalyst amount of 2.179 (g), reaction time of 57.45 min, reaction temperature of 59.91 °C, and MeOH/OMR of 5.9:1 (ml/ml), was validated in triplicate, and an average MOB yield of 98.03 (wt. %) was obtained. Results of XRD analysis indicated CaO as the predominant constituent element obtained from the mixture of calcined palm kernel shell husk (CPKSH) and calcined fermented kola nut husk (CFKNH). The qualities of MOB produced were within the biodiesel standard.

Investigation of ultrasound-assisted KOH and CaO catalyzed transesterification for biodiesel production from waste cotton-seed cooking oil: Process optimization and conversion rate evaluation

Development of Ultrasound (US)-assisted biodiesel production from Waste Cotton-seed Cooking Oil (WCCO) is gaining importance due to significantly lower reaction time and high energy-efficiency. In the present novel work, a comprehensive experimental study for KOH and CaO catalyzed transesterification process with detailed process optimization was performed. Kinetic modeling, scalability and energy analysis were performed to confirm the relative importance of US compared to Mechanical Stirring (MS). The optimized process parameters for KOH and CaO catalyst conditions were determined as methanol/oil molar proportion: 6.1:1 and 10.9:1, catalyst amount (w/w) %: 0.46 % and 0.96 %, reaction temperature: 53.2 °C and 48.3 °C, and the corresponding yield: 97.76 % ± 0.03 and 96.16 % ± 0.03 respectively. Box-Behnken model exhibits a significant correlation with experimental results in case of KOH (R2 = 0.98) and CaO (R2 = 0.97) catalyzed conditions. Triglyceride conversion follows pseudo-first-order reaction kinetics. The activation energy calculated for KOH and CaO catalyzed conditions was 21.36 and 33.83 kJ/mol respectively, which is 1.5 – 1.7 times lower as compared to MS process. Energy analysis showed that dissipated energy in US process is higher compared to MS. The scalability effect (with tenfold batch size), and ultrasonic duty cycle analysis showed that the continuous sonication is more effective in comparison to pulse mode. Physicochemical properties of produced biodiesel were observed in accordance with fuel specification as prescribed by ASTM D6751. Outcomes of this study are useful for development of energy-efficient US-assisted biodiesel production process on industrial scale.

A study on potential recovery of energy and value-added chemicals from in-situ pyrolysis of Bambusa balcooa over basic metal oxides

NiO and CaO catalysts with different weight percentages were used as catalysts in pyrolysis to investigate the feasibility of producing biofuels from Bambusa balcooa. Non-catalytic bio-oil was dominated by aromatic (23.74 %), acids (18.07 %), and alcohols (20.02 %) while optimized catalysts NiO and CaO increased the rate of ketonization in pyrolysis of Bambusa balcooa and decreased the mass yield of acids to 6.31 % and 9.06 % respectively. The quality of bio-oil obtained from catalytic tests was compared to the non-catalytic tests in terms of its product distribution, gasoline range hydrocarbon, viscosity, pH, flash point and fire point. It was observed that 0.5 wt.% NiO and 5 wt.% CaO contained a high yield of gasoline range hydrocarbon reaching 66.75 % and 73.47 %, respectively. In addition to the chemical composition, lower viscosity of the pyrolytic oil shows 0.5 % NiO as a better catalyst in pyrolysis systems to produce enhanced quality bio-oil.

Effect of dual-frequency pulsed ultrasonic excitation and catalyst size for biodiesel production

Biodiesel production with 6/2 pulsed ultrasonic single and dual frequencies were conducted under M/O molar ratio (9:1), CaO catalyst (size 200 mesh at 8%wt), time (37 min), intensity (0.91 W/cm2). Powers of waves were 140 W for single waves, and 70W + 70W for dual case. Biodiesel yield for dual frequency case was 96.16% while those of single 28 kHz and 40 kHz cases were 94.42% and 93.60% respectively. The power ratios were varied for the dual cases at 0/140, 20/120, 40/100, 60/80, 70/70, 80/60, 100/40, 120/20 and 140/0 W. The highest yield of 97.13% was obtained at 120/20 W. It was found that lower frequency waves played more important role than higher frequency. Thus, 28 kHz was used as the resonance frequency to determine the resonance size of the catalyst (equal to 49.50 μm). Lastly, biodiesel productions were conducted with 6/2 pulsed dual frequency waves (28 + 40 kHz, 120/20 W) and varying catalyst size as 150, 74, 38, 25 and 18 μm. The 38 μm size gave highest yield of 98.85% due to it was closer to the resonance size compared to the others. Thus using pulsed dual waves with optimal catalyst size can enhance the production yield from 93.60% to 98.85%.

Transesterfication Process of Waste Cooking Oil Catalyzed by Na/CaO Derived from Blood Clam (Anadara Granosa) Shells

Abstract: Blood clam (Anadara granosa) shells has the potential to be developed as a base heterogeneous catalysts for biodiesel production. Blood clam (Anadara granosa) shells has a high mineral content of calcium carbonate (CaCO3). CaCO3 can be decomposed into CaO at high temperature heating. In this study, CaO catalyst synthesized from the blood clam (Anadara granosa) shells calcined of 900 °C for 10 hours and then impregnated using NaOH (1, 3, and 5% w/w) the activation temperature of 600 °C for 5 hours. 3% Na/CaO catalyst was the most better catalyst with maximum biodiesel results obtained at 83,57% using the 3% Na/CaO catalyst. The maximum conditions obtained from biodiesel production using the 3% Na/CaO catalyst on the reaction temperature at 60 °C, the reaction time of 3.5 hours, stirring speed of 250 rpm, 3 g weight of catalyst, and the mole ratio of oil: methanol 1: 6.Keywords: Biodiesel, Transesterification, Blood clam shells, Heterogeneous base catalystReceived: 29 September 2019; Accepted: 2 December 2019; Published: 15 January 2020

Biodiesel production from used vegetable oil and CaO catalyst impregnated with KNO<sub>3</sub> and NaNO<sub>3</sub>

The rise in global energy demand has encouraged exploring into other innovative methods of generating renewable fuels from different forms of waste. Due to its accessibility, culinary used vegetable oil is regarded as a potential source for profitable production of biodiesel. In the present study, the viability of producing biodiesel from used vegetable oil (UVO) by utilizing CaO catalyst (derived from the calcination of chicken eggshell and impregnated with KNO₃ and NaNO₃) was studied. Higher yield of biodiesel was obtained at methanol/oil mole ratio of (9–10) and CaO catalyst concentration of (2.0–3.0) wt/wt% Oil, for the three forms of catalyst used. Also, higher yield of biodiesel was obtained when CaO with impregnated KNO₃ was used, followed by the operation involving CaO with impregnated NaNO₃. At optimum conditions of methanol/oil mole ratio of 9 and catalyst concentration of 2.4 wt/wt% Oil, the yields of biodiesel obtained were 90% (for unimpregnated catalyst), 92% (using CaO impregnated with NaNO₃) and 95% (using CaO impregnated with KNO₃). The higher biodiesel yield obtained for CaO impregnated with KNO₃ (compared to the yield from CaO impregnated with NaNO₃) could be traced to a more reactive nature of potassium and arrangement of electrons of both potassium and sodium. The results of the tests and analysis on biodiesel properties reveal that quality biodiesel were produced from the three forms of catalyst used. This is because, each of the values of the properties considered falls within the ASTM standard.

Concentration of cao catalyst from chicken eggshell in transesterification process of pangi seed oil biodiesel

The purpose of this research was to obtain best consentration of CaO catalyst chicken eggshell in transesterification process on quality of biodiesel produced from pangi seed oil. The treatment of CaO catalyst concentrations in this research was S1 (1%), S2 (1.5%), S3 (2%), S4 (2.5%), and S5 (3%). The collected data were statistically analyzed by using Analysis of Variance (ANOVA) continued by Duncan’s New Multiple Range Test (DNMRT) test at 5% level. The parameters observed were acid value, density, iodium value, saponification value, and cetana number. The results of analysis showed that consentration of CaO catalyst chicken eggshell gave unsignificantly affect on acid value and cetana number but significantly affect on density, iodium value, and saponification value of biodiesel. The chosen treatment in this research was S5 (CaO catalyst 3%). The treatment of S5 has yield 97.99% with characteristics acid value 0.68 mg KOH/g, density 885.22 kg/m3, iodium value 81.41 g I2/100 g, saponification value 179.00 mg KOH/g, and cetana number 58.48. A post-publication change was made to this article on 11 Mar 2020 to correct the conference title in the PDF header.

Production of Biodiesel from Nyamplung (Calophyllum inophyllum L.) using Microwave with CaO Catalyst from Eggshell Waste: Optimization of Transesterification Process Parameters

AbstractFossil fuel is the main energy resource in Indonesia with oil as the dominant fuel (44.1% of primary energy consumption) in 2017. But fossil fuel is not environmentally friendly and non-renewable. Thus, there is a need for alternative renewable fuels such as biodiesel. Biodiesel from nyamplung (Calophyllum inophyllum L.) oil can provide a promising future as a renewable fuel resource. The used of CaO catalyst from eggshell waste is also profitable, and microwave radiation can help the biodiesel production process run more effectively. Optimization of parameters such as microwave power, catalyst concentration, and transesterification time was performed by using Box-Behnken design. Combinations between biodiesel production from nyamplung oil with CaO catalyst using microwave and treated with Box-Behnken design is considered a new and modern method with optimization of the parameters which affect the transesterification process. The result showed that at a microwave power of 325.24 W, a concentration of catalyst of 3.88%, and a transesterification time of 12.47 min can produce an optimal yield of biodiesel of 98.9079% with the reliability of 92.37%.

Effect of Ce/Ca Ratio in Ni/CeO2-ZrO2-CaO Catalysts on High-Purity Hydrogen Production by Sorption-Enhanced Steam Reforming of Acetic Acid and Bio-Oil

The sorption-enhanced steam reforming (SESR) of poplar sawdust pyrolysis oil and acetic acid for high-purity hydrogen production was investigated in this present work. The Ni/CeO2-ZrO2-CaO bifuncti...

Hydrothermal co-gasification of sorghum biomass and çan lignite in mild conditions: An optimization study for high yield hydrogen production

In this study, response surface methodology (RSM) combined with a 3–factor and 3–level Box–Behnken design (BBD) was performed to obtain high yield hydrogen production from hydrothermal co–gasification of sorghum biomass and low rank Çan lignite in a batch type reactor at 500 °C. The individual and the combined effects of the process parameters of coal amount (%) of the coal/biomass mixtures, initial water volume (mL) of the reactor and amount of the coal/biomass mixtures (kg) on system pressure, total gas yield, hydrogen production and product distribution were determined. Water volume directly affected the system pressure and the reaction medium was supercritical water medium above 48.2 mL with a pressure of 22.06 MPa. The highest values of both total gas volume and hydrogen gas volume were reached by gasification of 5.0 g of feedstock. It has been observed that total gas volume and hydrogen volume were directly affected by the water volume in the reactor and the coal ratio of the coal-biomass mixtures. The highest total gas and hydrogen volumes can be achieved under the conditions where the higher levels of water volume of the reactor and lower levels of coal percentage of the coal/biomass mixture were combined. Optimum conditions for maximum hydrogen production with 5.0 g of coal/biomass mixture were determined with numerical optimization as coal percentage of 25.6% and initial water volume of 68.5 mL. By combining the impregnated K2CO3 (3%, (w/w)) and CaO catalysts an excellent hydrogen selectivity was achieved. The hydrogen selectivity was drastically increased from 32.0% to 70.8% by capturing more than 99% of CO2 with a H2/CO2 mol ratio of 88.5.

Production of an upgraded bio-oil with minimal water content by catalytic pyrolysis: Optimisation and comparison of CaO and MgO performances

Pyrolysis of forest residues using CaO and MgO catalysts was carried out in an induction heating reactor, to produce an upgraded bio-oil with increased higher heating value (HHV). Optimisation with central composite design (CCD) included temperature (444−656 °C) and catalyst concentration (1.7–58.3 wt.%). A fractional condensation system with the first condenser heated to 40 °C was used to collect an organic-rich oil. The optimum HHV of the oil was 26.9 MJ/kg (560.0 °C and 33.8 wt.% catalyst) at 19.4 wt.% yield with MgO and 26.4 MJ/kg (550.0 °C and 30.0 wt.% catalyst) at 18.9 wt.% yield with CaO (based on a desirability function used to obtain significant oil yield). The combination of water-gas shift reaction (WGSR) catalysed by CaO and the fractional condensation system resulted in water content of the oil at the optimum of only 7.8 wt.%. Absorption of CO2 by CaO, together with significant H2 production (400 % increase compared to non-catalytic case) allowed the production of a gas calorific value of 13.7 MJ/kg compared to 5.2 MJ/kg without catalyst.

Catalytic pyrolysis of wasted fishing net over calcined scallop shells: Analytical Py-GC/MS study

Activity of calcined scallop shell (CSS) for the catalytic pyrolysis of wasted fishing net (WFN) to the ε-caprolactam monomer was investigated in a micro-furnace type temperature programmable pyrolyzer combined with a gas chromatography/mass spectrometry (Py-GC/MS) analysis system. Evolved gas analysis (EGA/MS) indicates that the peak temperature for the decomposition of WFN in the absence of catalysts was around 420−480 °C whereas the temperature decreased down to 380−420 °C in the presence of CSS or commercial CaO catalysts. The yield of ε-caprolactam reached 66 wt.% in a catalytic depolymerization condition at 410 °C for 2 min with a 1:5 WFN/CSS weight ratio by using the Py-GC/MS system. Based on these experimental results, CSS should be an alternative catalyst for the recovery of the ε-caprolactam monomer from the WFN.

New route for the synthesis of silica-supported calcium oxide catalyst in biodiesel production

This research aims to investigate the role of silica as a support for CaO catalyst in 4 different aspects: determination of optimum parameters, tolerance of water and FFA content, leaching and kinetics evaluation, and reusability of catalyst. Silica was extracted from rice husk by ion exchange method and subsequently impregnated with CaO. The experimental results showed that the supported catalysts exhibit excellent catalytic activity in transesterification of waste cooking oil with high yield of biodiesel, comparable to that of CaO catalyst. This is due to the fact that catalyst with higher surface area produces higher biodiesel yield. The presence of water did not have significant effect on the performance of supported catalysts, as silica can act as catalyst to esterify the FFA. Furthermore, silica support offered the greatest extent of leaching minimization of CaO and it has been proved that the calcium leached species was insignificant in transesterification reaction. Reusability study suggests that the synthesized catalysts can be recycled up for 8 successive runs. In conclusion, employing calcium rich wastes derived CaO impregnated with silica as catalyst showed good potential in catalytic applications with high economic benefits.

Upgrading of bio-oil via microwave-assisted pyrolysis of corncob over CaO and HZSM-5 mixed catalysts to promote the formation of aromatic hydrocarbons

Bio-oil upgrading via microwave-assisted pyrolysis of corncob over CaO and HZSM-5 mixed catalysts to promote the formation of aromatic hydrocarbon was investigated in this study. Results showed that with an increased ratio of HZSM-5 catalyst, the bio-oil yield was decreased; however, the proportion of aromatic hydrocarbons increased at first and then decreased. The maximum proportion of aromatic hydrocarbons was 35.8%, which was obtained with an optimal ratio of CaO to HZSM-5 of 1:2. This study showed the effects of CaO and HZSM-5 mixed catalysts under microwave-assisted pyrolysis in terms of improving the formation of aromatic hydrocarbons in bio-oil.

Immobilization of calcium oxide onto polyacrylonitrile (PAN) fibers as a heterogeneous catalyst for biodiesel production

We describe the design, creation, and usage of a CaO catalyst immobilized onto polymeric mats for environmentally-friendly biodiesel production. The polyacrylonitrile (PAN) fiber mats were prepared by electrohydrodynamic processing (EHD), commonly known as electrospinning or electrospraying, in which immobilized CaO particles were either physically entrapped on the fibers or chemically bound onto the fiber surface by a dopamine linkage. These two catalyst materials were later successfully used in the transesterification of fresh canola oil into biodiesel. Mechanically entrapped CaO particles in the PAN fibers were able to be re-used up to six times in the conversion of triglycerides into biodiesel, while the chemically immobilized catalyst was found impossible to reuse. The use of EHD processing allows us to create an easily separable, reusable catalyst that could be commonly used in transesterification reactions.

Characterization of methyl ester compound of Carica papaya seed oil through Transesterification using CaO Catalyst from Strombus canarium shells

Biodiesel is an alternative fuel that is included in renewable energy. Various problems of the source of raw materials for making biodiesel create an opportunity to find alternative sources of raw materials from plant oils, one of which is papaya seeds. Extraction of papaya seeds into oil is carried out by socletation and distillation methods. GCMS analysis showed that papaya seed oil contained oleic acid. Biodiesel transesterification has been carried out using CaO catalyst from the Strombus canarium shells. The reaction was carried out at the papaya seed oil to methanol molar ratio of 1: 6, presence catalyst 5% wt relative to oil and temperature reaction of 65 °C for 2 h. GC/MS analysis result showed that the content of methyl esters is 50.35% with the highest abundance is 10-Octadecenoic acid and the smallest abundance is 9-Octadecenoic acid.

Biodiesel production from waste cotton-seed cooking oil using microwave-assisted transesterification: Optimization and kinetic modeling

The current research focuses on process optimization and kinetic study of microwave-assisted transesterification process using KOH and CaO catalyst from waste cotton-seed cooking oil (WCCO). In order to enhance the biodiesel yield, process parameters: methanol to oil ratio (A), catalyst loading (B) and reaction time (C) were optimized by applying response surface methodology based on full factorial design method. It was found that for KOH catalyzed condition, the optimum values for A, B and C are 7:1, 0.65 (w/w) % and 9.6 min, respectively and the model predicted yield is 96.44%. For CaO catalyzed condition, the optimum values for A, B and C are 9.6:1, 1.33 (w/w) % and 9.7 min, respectively and the predicted yield is 89.94%. Experiments were performed using the optimized parameters and the mean biodiesel yield determined for KOH and CaO catalyzed conditions are 96.55 ± 0.23% and 90.41 ± 0.02%, respectively which shows good agreement with model predictions. Analysis of perturbation plots showed that catalyst loading is the most sensitive variable. Considering pseudo-first-order kinetic, the activation energies were obtained and found to be 13.05 kJ mol-1 and 28.93 kJ mol-1 respectively for KOH and CaO catalyzed conditions. The activation energy observed for microwave-assisted method are significantly lower compared to that of conventional method. The scale-up study (with 10 fold batch-size) and energy analysis have been done for KOH and CaO catalyzed conditions whereas reusability was performed with CaO catalyst. It was observed that up to four cycles the biodiesel yield achieved was more than 90%. In microwave-assisted process, efficency factor found to be higher as compared to conventional method. The produced biodiesel properties fulfill fuel specifications designated as per ASTM D6751 standard. The outcome of microwave-assisted transesterification study enhances biodiesel yield and significantly decreases the reaction time, thus making it energy-efficient technique.

Experimental study on gasification of bituminutesous coal char with CO2 catalysed by CaO

The effects of CaO under normal pressure and CaO soaked in ammonia on the isothermal gasification of Jinjie bituminous coal char-CO2 are studied on the self-built fixed-bed experimental bench with analytical pure CaO as the precursor. The experimental results show that the gasification activity of Jinjie coal char increases with the increase of Ca addition. The load saturation is 5% at 780°C gasification temperature, and the load saturation are 3% at 810°C, 850°C and 900°C. Adding 3% CaO coal char can reduce the gasification temperature by 120°C, and reduce the coal char conversion rate to 95% by 85 min at 900°C gasification temperature. After soaking in ammonia water, the gasification activity of coal char and the gasification activity of coal char added with CaO catalyst are increased to different degrees. At 850°C, the increase of K value and Rm reach the maximum when CaO catalyzes coal char gasfication by ammonia immersion, which are 49.7% and 35.9%, respectively.

Kinetika Reaksi Transesterifikasi Minyak Kedelai Menjadi Biodiesel dengan Katalis CaO

The use of biodiesel is expected to reduce dependence on fossil fuels. In this study, the kinetic reaction of transesterification of soybean oil with methanol will be assessed using heterogeneous CaO solid base catalyst with parameters of mole ratio of reactants to the conversion of methyl ester used to determine the reaction velocity equation. The reaction speed equation is used in the design of a fluidized CSTR (Continues Tank Reactor) reactor to obtain the reactor volume and catalyst weight. The purpose of this study was to determine the form of the velocity reaction equation for soybean and methanol transesterification reactions using CaO catalyst and determine the weight of the catalyst needed by using the reaction speed equation. The study was carried out by transesterification of soybean oil and methanol with CaO catalyst with the independent variable mole ratio of reactants while the fixed variable reaction temperature was 60°C, catalyst weight was 3% (% b/v), reaction time was 180 minutes. The results showed that methanol adsorbed on the surface of the catalyst and triglycerides not adsorbed on the surface of the catalyst showed that the mechanism of the catalytic reaction that occurred was the Eley-Rideal mechanism where one of the reactants was adsorbed on the surface of the catalyst. The form of the speed equation for the transesterification reaction of soybean oil and methanol using a CaO catalyst is . The reaction speed equation is used in the design of the reactor, so that the relationship between the weight of the catalyst needed to convert triglycerides to biodiesel and the predicted calculation of the volume of the reactor used can be done.