Heterogeneous Catalyst For Biodiesel Production Research Articles

Qualitative role of heterogeneous catalysts in biodiesel production from Jatropha curcas oil

Biodiesel properties are in general attributed to the composition and properties of the oil feedstock used, overlooking the possible impacts of the catalyst preparation details. In light of that, the impacts of different catalyst preparation techniques alongside those of different support materials on the yield, composition, and fuel properties of biodiesels produced from the same oil feedstock were investigated. More specifically, tri-metallic (Fe-Co-Ni) catalyst was synthesized through two different techniques (green synthesis and wet impregnation) using MgO or ZnO as support material. The generated catalyst pairs, i.e., Fe-Co-Ni/MgO and Fe-Co-Ni/ZnO prepared by wet impregnation and Fe-Co-Ni-MgO and Fe-Co-Ni-ZnO prepared by green synthesis (using leaf extracts) were used in the transesterification process of Jatropha curcas oil. Detailed morphological properties, composition, thermal stability, crystalline nature, and functional groups characterization of the catalysts were also carried out. Using Box-Behnken Design response surface methodology, it was found that the green-synthesized Fe-Co-Ni-MgO catalyst resulted in the highest biodiesel yield of 97.9%. More importantly, the fatty acid methyl ester (FAME) profiles of the biodiesels produced using the four catalysts as well as their respective fuel properties were different in spite of using the same oil feedstock.

CaO/Natural Dolomite as a Heterogeneous Catalyst for Biodiesel Production

In the present study, the CaO/Natural Dolomite as a heterogeneous catalyst was applied to synthesize biodiesel from coconut oil. The physico-characteristics of CaO/Natural Dolomite catalyst were determined using X-ray diffraction (XRD), X-Ray Fluorescence, and porosity analysis (specific surface area, average pore size diameter and total pore volume). The performance of CaO/Natural Dolomite catalyst was examined in a batch reactor for transesterification reaction of coconut oil with methanol. From the experiments, the optimum process conditions were achieved at a 60°C of reaction temperature, a 5 wt.% of catalyst amount, and 6 : 1 of methanol to coconut oil mass ratio. The CaO/Natural Dolomite catalyst exhibits high catalytic activity and reliable to be applied in biodiesel synthesis as a heterogeneous base catalyst.

Bifunctional Heterogeneous Catalyst for Biodiesel Production from Waste Vegetable Oil

Bifunctional solid catalysts facilitate the esterification of free fatty acids (FFA) into alkyl esters alongside the transesterification reaction, which allows for the use of waste vegetable oils with high water and FFA contents for biodiesel production. This makes the process economically viable and greener, as the waste fats and oils are readily available. The concurrent esterification and transesterification of waste palm oil (WPO) and waste sunflower oil (WSO) with methanol was investigated in the presence of calcium oxide on alumina catalyst in a conventional batch process. The catalyst characterization showed the existence of calcium oxide aluminates (calcined at 750 °C), which exhibited crystalline phases with porous/spongy-like particles. The high concentration of CaO in CaO/Al2O3 was a favorable support material in the heterogeneously-catalyzed transesterification reactions. The optimum catalyst parameters for the production of fatty acid methyl esters (FAMEs) were observed at 65 °C for 4 h with a methanol-to-oil ratio of 9:1, 60% (waste palm oil, or WPO) and 80% (waste sunflower oil, or WSO), CaO/Al2O3 (% wt/wt) catalyst ratio as well as 4% CaO/Al2O3 concentration (% wt.) for WSO and WPO. The simultaneous esterification/transesterification reactions at optimum conditions on WPO and WSO led to high yield of FAMEs of 89, 61 and 55% for WPO and 54, 75 and 98% for WSO at catalyst ratios (wt %) of 60, 70 and 80% respectively. The use of bifunctional heterogeneous catalyst (CaO/Al2O3) with waste vegetable oil can result in high performance and the upscaling of biodiesel production.

Development of Sulphonated Sago Pith Waste Catalyst for Esterification of Palm Fatty Acid Distillate to Methyl Ester

Biodiesel is considered as one of the renewable sources of energy that has been highlighted as an alternative fuel due to its versatile properties. Despite the fact that it is remarkable, there are several issues such as its industrial production cost and environmental concern related to the usage of homogenous catalyst. Among the alternatives are to switch to use Palm Fatty Acid Distillate (PFAD) as a low-cost feedstock and utilizing a heterogeneous Sago Pith Waste (SPW) catalyst. In this study, the heterogeneous catalyst was prepared by sulfonating the incomplete carbonized SPW under various preparation conditions. One factor at a time (OFAT) method was carried out to determine the optimum preparation condition for sulfonated SPW catalyst and the produced catalysts were characterized to study its morphology, crystallinity, surface area and acid density. The optimum preparation condition for sulfonated SPW catalyst were 1:20 ratio mass of dry SPW to the volume of sulfuric acid, 5 minute of sulfonation time and 200 °C of carbonization temperature. The optimum catalyst prepared gave 99.34 % methyl ester yield and 93.03 % PFAD conversion. Substantial yield and conversion obtained indicated the suitability of SPW as a heterogeneous catalyst for biodiesel production.

Biodiesel production from Kesambi (Schleichera oleosa) oil using multi-walled carbon nanotubes supported zinc oxide as a solid acid catalyst

The development of heterogeneous catalysts for biodiesel production became a hot topic among scientists because of its many advantages including easy separation and catalyst reusability. In this study, multi-walled carbon nanotubes supported zinc oxide (MWCNTsZ) as a solid acid catalyst had been successfully prepared via the stober-like process. There are several % loading of ZnO variations ranging from 10 – 35 % of catalyst weight. These catalysts were characterized by x-ray diffraction (XRD), BET surface area analysis, and scanning electron microscope with energy-dispersive x-ray spectroscopy (SEM-EDX) analysis. Transesterification of kesambi (Schleichera oleosa) oil also had been done to test the activity of the solid catalyst. The potential of this catalyst is shown from its large surface area with the maximum surface area until 409 m2/gram. However, the quantity of dispersed zinc oxide (ZnO) on multi-walled carbon nanotubes (MWCNTs) via that modified Stober preparation is quite small lower than 5% weight. This phenomenon is resulting in a low yield of biodiesel after 3 h of transesterification reaction. The highest yield of biodiesel is obtained with 20% weight of loading ZnO variable producing 13.82% yield of methyl ester.

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

Hybrid CaO/Al2O3 aerogel as heterogeneous catalyst for biodiesel production

We report a new hybrid CaO/Al2O3 aerogel and its application as a heterogeneous catalyst for the production of biodiesel. These catalysts were successfully prepared for the first time via the rapid epoxide-initiated sol-gel process and dried under supercritical carbon dioxide conditions. The catalytic activity has been investigated under various conditions for the transesterification reaction of a waste cooking oil in the presence of methanol. The catalysts were characterized by FTIR spectroscopy, nitrogen adsorption-desorption technique, scanning electron microscopy, and powder X-Ray diffraction. The calcined aerogels at low CaO content were not as affected by calcination at 700 °C as their corresponding calcined alcogels and they revealed distinct structures, porosities, surface areas, and morphologies. The 3:1 CaO/Al2O3 calcined aerogel showed the best catalytic activity using the minimum amount of catalyst to produce high biodiesel yield and conversion with no soap formation. The effect on biodiesel production of calcium-to-aluminum molar ratio, catalyst loading, methanol-to-oil molar ratio, and reaction time was investigated. At optimal conditions, a maximum biodiesel yield (89.9%) with high purity (98.0%) was achieved and the transesterification reaction was found to follow pseudo-first-order kinetics. The optimal conditions are 1 wt% 3:1 CaO/Al2O3 calcined aerogel for reactions performed at 65 °C over 4 h using a methanol-to-oil molar ratio equal to 11:1.

Utilization of water hyacinth-based biomass as a potential heterogeneous catalyst for biodiesel production

With the aim to reduce the negative impacts caused by the widespread of water hyacinth to the environment, this paper reports the utilization of water hyacinth as a source of biomass to fabricate a heterogeneous catalyst. The catalyst was prepared by calcinating the grounded hyacinth biomass at 600°C, and K2CO3 was then introduced as a co-catalyst through impregnation method. The properties of biodiesel were also evaluated in terms of yield and density. To better understand the impregnation effects, surface topography, particle size, and atom composition of water hyacinth catalyst with K2CO3 impregnation were analysed. The performance of the synthesized catalyst was studied for the transesterification reaction of palm oil into biodiesel. The reaction was carried out in a batch mode for 3 hours with stirring at 65°C. The molar ratio of methanol to the oil of 12:1, and the catalyst loading was 15 wt. %. The highest yield (97.57%) was obtained from the process using 15% of the hyacinth-based catalyst which impregnated with 10% of K2CO3. The biodiesel produced was in the range of the SNI standard. The water hyacinth can be a promising heterogeneous catalyst for biodiesel production at an industrial scale.

The Roles of the Structure and Basic Sites of Sodium Titanates on Transesterification Reactions to Obtain Biodiesel

Sodium titanates were evaluated as heterogeneous catalysts for biodiesel production. Materials were prepared using an experimental design considering NaOH and TiO2 concentrations and hydrothermal and calcination temperatures as input variables. Materials characterization was carried out by DRX-Rietveld refinement, CO2-TPD, and XPS. Statistical analysis of the experimental results indicates that the calcination temperature is the most influential factor in the formation of sodium titanates with high catalytic performance in transesterification reactions. Further analysis of the oil-to-biodiesel conversion revealed that the catalytic activity of sodium titanates is directly correlated to the catalyst associated species and to the density of medium-strong basic sites on the surface of the material, obtaining up to 95% conversion to biodiesel at 60 °C using 3.6% weight catalyst with respect to oil.

High operative heterogeneous catalyst in biodiesel production from waste cooking oil

Our work aims to produce a new catalyst that was a highly operative in the production of biodiesel from waste cooking oil WCO. A heterogeneous solid acid catalyst (RS-SO3H) was prepared by fast pyrolysis of rice straw, then it was followed by a sulfonation process. It was formed by using concentrated sulfuric acid. The Fourier transform infrared spectroscopy (FTIR) analysis confirmed that the chemical structure consists of sheets of amorphous carbon with hydroxyl and carbonyl (OH and COOH) groups as well as high density of SO3H. The surface area of RS–SO3H and the average pore size were characterized by scanning electron microscopy (SEM) and surface area analyzer. The results of Thermogravimetric analysis (TGA) showed that RS–SO3H has favorable thermal stability. Conventional energy sources were exhausted. So, we examined the catalyst activity on developing alternative energy resources, It became more imperative and environment friendly. WCO is attracting increased attention in the biodiesel production by transesterification process. The factors affecting the transesterification process include reaction time and temperature, catalyst concentration and methanol: oil molar ratio, were studied. The maximum mass yield of biodiesel extended to 90.37%. The content of fatty acid methyl ester (FAME) is around 97.71 wt%, conversion efficiency% of raw material reached 90.38 wt% and %free fatty acid (%FFA) conversion was 91.1% at optimum conditions: 10 wt% catalyst using methanol: oil molar ratio (20:1) at 70 °C for 6 h. The FAME content% was determined by gas chromatography (GC). The physicochemical properties of the biodiesel produced are close to the commercial diesel and the ASTM standards biodiesel D6751. The reusability of the used catalyst indicated that the catalyst was highly operative in production biodiesel. Where % conversion efficiency of raw oil under optimized conditions decreased from 90.37 to 88.56% after 8 cycles. The %FFA conversion was constant around 91.1% until 7 runs then it decreased.

A Series of UiO-66(Zr)-Structured Materials with Defects as Heterogeneous Catalysts for Biodiesel Production

As a result of the demand overload for energy and elevating the prices of crude oil, countries are seeking for finding alternative energy sources. Biodiesel (mono alkyl ester) is an ideal candidate...

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.

Synthesis and modification of mesoporous silica with sulfated titanium dioxide as a heterogeneous catalyst for biodiesel production from palm fatty acid distillate

This study synthesizes fatty acid ethyl ester (FAEE) through esterification reaction of palm fatty acid distillate (PFAD) using SO42−/TiO2 supported by mesoporous silica as a catalyst. The steps of this study were a synthesis of mesoporous silica, catalyst preparation by impregnation and catalyst activity test through esterification reaction of PFAD by using ethanol. The variables of study on the esterification reaction were the weight ratio of catalyst and PFAD as 3%, 5%, 7%. Based on BET characterization, it shows that synthesized silica material is mesoporous silica. The characterization result of silica and catalyst using X-Ray of wide-angle powder (WAXRD) and SEM gives information that the existence of silica as support of SO42−/TiO2 active site. At the catalyst activity test through esterification reaction, it was obtained the best weight ratio of catalyst and PFAD was 5% with the conversion of ethyl ether formation as 98.9 %. Analysis data and physical properties were viscosity at a temperature of 40 °C and density at the temperature of 15 °C, it shows that the value fit a biodiesel standard of ASTM, meanwhile analysis data of GC-MS toward product of ethyl ester and PFAD has shown that most of the fatty acid in PFAD had been converted into ethyl ester.

Highly crystalline heterogeneous catalyst synthesis from industrial waste for sustainable biodiesel production

Iron and steel factories in Egypt have been suffering from fine calcium oxide (CaO) emission which is considered as a waste and leads to many health hazards. An alternative, this waste (fine CaO) has been utilized as a low-cost, sustainable source of calcium sulfate impregnated sulfated silica (CSISS) nano-catalyst production. This hybrid catalyst has been utilized as a heterogeneous catalyst for biodiesel production from waste frying oil (WFO). In this study, the linear, quadratic and interaction effects of the main four factors that affect the biodiesel yield were investigated. An empirical model has correlated the experimental results and used to optimize and predict the biodiesel production yield. The model showed good agreement of about 93% with the experimental results and revealed that the optimum operating condition is: 50% SiO2 content, 20 min reaction time, 8:1 methanol to oil molar ratio and 3% catalyst weight at 55oC and 300 rpm stirring speed to produce 99% biodiesel yield. The physicochemical properties of the produced biodiesel were analyzed. The combustion exhaust emissions of the produced biodiesel / petrodiesel blends have been evaluated. The techno-economic analysis elucidated that, the produced biodiesel is a strong competitor to petrodiesel with a cost of US$0.488/L.

Carica papaya stem: A source of versatile heterogeneous catalyst for biodiesel production and C–C bond formation

Development of solid mixed oxide catalyst from waste biomass is a scarcely studied area. Thus, present protocol aims to prepare an environmentally friendly, efficient, renewable and recyclable heterogeneous base catalyst from Carica papaya stem. The chemical and structural properties of the catalyst were examined by Fourier-transform infrared spectroscopy (FTIR), X-ray diffractograms (XRD), Scanning electron microscopy (SEM), Energy Dispersive X-ray spectrometry (EDX), Transmission Electron Microscopy (TEM) and Brunauer-Emmett-Teller (BET) analysis. The CO2-TPD and Hammett indicator test was conducted to determine the basicity of the prepared catalyst. The study revealed the presence of alkali and alkaline earth metals that provide the basic sites to facilitate transesterification reaction for biodiesel production and formation of benzylidenemalononitrile (BMN). The conversion of the waste cooking oil (WO) and Scenedesmus obliquus (SO) lipid to biodiesel was confirmed by the NMR and Gas chromatography Mass Spectroscopy (GC-MS) technique. Biodiesel conversions of 95.23% and 93.33% were achieved using 2 wt % catalyst loading under optimized reaction conditions for WO and SO respectively. Reusing the catalyst showed a slight drop in activity after 6 repeated uses. The reported catalyst has shown its potential as an alternative and cheaper green solid catalyst for biodiesel production and Knoevenagel reaction.

Low-energy synthesis of kaliophilite catalyst from circulating fluidized bed fly ash for biodiesel production

Circulating fluidized bed fly ash (CFBFA) was used to synthesize kaliophilite catalyst via a facile and low-energy two-step process: fabrication of amorphous CFBFA geopolymer and hydrothermal transformation of CFBFA-based geopolymer into kaliophilite. X-ray diffraction and scanning electron microscopy results demonstrated that CFBFA was successfully converted into kaliophilite with short prismatic crystals having size of ~1 μm. Temperature-programmed desorption of CO2 analysis results indicated the presence of abundant weak, medium-strength and high-strength basic sites on the kaliophilite catalyst, which were respectively assigned to hydroxyl groups, K-O ion pairs, and O2− ions. When kaliophilite was used as a heterogeneous catalyst for biodiesel production, the highest biodiesel yield of 99.2% was obtained under transesterification conditions of 5 wt% catalyst concentration, methanol:canola oil mole ratio of 15:1, reaction temperature of 85 °C, and reaction time of 6 h. The kaliophilite catalyst could be easily recovered and reused for four cycles without significant deactivation. Further, a solid base catalysis mechanism for transesterification over kaliophilite catalyst was proposed.

Application of magnetic alumina-ferric oxide nanocatalyst supported by KOH for in-situ transesterification of microalgae cultivated in wastewater medium

Nowadays, use of microalgae as a cheap feedstock and heterogeneous catalysts for biodiesel production has gained considerable interest as they mitigate environmental problems induced by the conventional process of biodiesel production using homogeneous alkali catalysts. However, separation of heterogeneous catalysts from tissues and carcass of microalgae is an important task. For this reason, a magnetic Fe2O3–Al2O3 nanocatalyst promoted by potassium groups was synthesized using a modified impregnation method and was profoundly studied and compared with nanocatalysts without ferric oxide using X-ray diffraction, Fourier-transform infrared, Brunauer-Emmett-Teller and Barrett-Joyner-Halenda, scanning electron microscopy, transmission electron microscopy and energy-dispersive spectroscopy analyses. The results revealed that the magnetic nanocatalyst with a core-shell structure had suitable surface area, pore size, and particle size and also had no impurity on its structure. The nanocatalyst was used for biodiesel production from microalgae cultivated in a wastewater medium via in-situ transesterification reaction. The nanocatalyst converted 95.6% of microalgae lipids to esters at optimum conditions of 65 °C, 12 mL g−1 of methanol-to-dry biomass, 4 wt% of magnetic catalyst and 6 h of reaction time. The magnetic K/Fe2O3–Al2O3 core-shell nanocatalyst was reused for several times and presented high stability with less reduction in its activity until six runs.

Rapid esterification of fatty acid using dicationic acidic ionic liquid catalyst via ultrasonic-assisted method.

Biodiesel production via esterification/transesterification reactions can be catalyzed by homogenous or heterogeneous catalysts. Development of heterogeneous catalysts for biodiesel production is highly advantageous due to the ease of product purification and of catalyst recyclability. In this current work, a novel acidic [DABCODBS][CF3SO3]2 dicationic ionic liquid (DIL) was used as heterogeneous catalyst to produce biodiesel using oleic acid as model oil. The esterification was conducted under ultrasonic irradiation (20 kHz) using a 14 mm ultrasonic horn transducer operated at various duty cycles. It was observed that the duty cycle, amplitude, methanol to oil molar ratio, catalyst amount and reaction temperature were the major factors that greatly impact the necessary reaction time to lead to a high yield of biodiesel. The reaction conditions were optimized with the aid of Response Surface Methodology (RSM) designed according to the Quadratic model of the Box Behnken method. The optimum conditions were found to be at catalyst amount of 0.64 mol%, methanol to oil ratio of 14.3:1, temperature of 59 °C, reaction time of 83 min and amplitude of 60% in continuous mode. The results showed that the oleic acid was successfully converted into esters with conversion value of 93.20% together with significant reduction of reaction time from 7 h (using mechanical stirring) to 83 min (using ultrasonication). The results also showed that the acidic DIL catalyst we designed purposely was efficient to catalyze the ultrasonic-assisted esterification yielding high conversion of oleic acid to methyl oleate on short times. The DIL was also recycled and reused for at least five times without significant reduction in performance. Overall, the procedureoffersadvantages including short reaction time, good yield, operational simplicity and environmentally benign characteristics.

The enhanced activity of base metal modified MgAl mixed oxides from sol-gel hydrotalcite for ethylic transesterification

MgAl hydrotalcite was successfully prepared through the sol-gel method and modified by in situ addition of base metals (Me = K, Ba, Sr and La). The Me–MgAl hydrotalcites were calcined and the obtained oxides were evaluated as catalysts for ethylic transesterification in order to investigate their potential application for biodiesel production. The Me–MgAl characterization revealed that the materials present different crystalline structures and the metal addition caused surface area reduction and increased the apparent crystallite size. On the other hand, the addition of the base metals to hydrotalcite deeply affected the base properties of the oxides, increasing their catalytic activity. Particularly, the Ba–MgAl presents the highest amount of strong base sites which resulted in a high conversion (≈90%) in the model transesterification reaction between methyl acetate and ethanol. Furthermore, an ester conversion of about 80% was reached in soybean oil transesterification. Moreover, the Ba–MgAl can be reused for 3 batch cycles with low deactivation. These results suggest that Ba–MgAl can be considered a promising heterogeneous catalyst for biodiesel production.

The synthesis of biodiesel using copper based metal-organic framework as a catalyst

The metal-organic framework (MOF) used as a heterogeneous catalyst for biodiesel production has been produced from the coordination of benzene-1,3,5-tricarboxylic acid (BTc) and divalent copper (Cu). A straightforward solvothermal method with ethanol-water solvent was employed for the production of MOF, and rod-like CuBTc-MOF particles with a unit cell length of 37.12 nm were obtained. Brunauer–Emmett–Teller (BET) sorption-isotherm characterization revealed that CuBTc holds a surface area of 1085.72 m2/g and a total pore volume of 1.68 cm3/g. The high thermal stability of CuBTc, with a degradation temperature of 303 °C, was confirmed through thermogravimetric analysis (TGA). Other characterizations were also carried out to characterize the CuBTc. Specifically, Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and X-ray diffraction (XRD) analysis. The produced CuBTc-MOF is applied to produce biodiesel from palm oil. The composition in biodiesel was quantified using gas chromatography (GC) analysis. The optimal FAME yield in biodiesel of 91% was obtained from transesterification using 0.04 g CuBTc and methanol to oil volume ratio of 5:1. Recycled CuBTc- MOF was also capable of producing biodiesel with high FAME yield, which is 86%. The obtained result signifies the potential catalytic activity of CuBTc-MOF in the production of biodiesel.