Catalyst For Transesterification Reaction Research Articles

Conformation Analysis of T1 Lipase on Alcohols Solvent using Molecular Dynamics Simulation

Biodiesel usually is produced commercially via a transesterification reaction of vegetable oil with alcohol and alkali catalyst. The alkali catalyst has some drawbacks, such as the soap formation during the reaction. T1 Lipase enzyme had been known as a thermostable biocatalyst which is able to produce biodiesel through a cleaner process. In this paper the performance of T1 lipase enzyme as catalyst for transesterification reaction in pure ethanol, methanol, and water solvents were studied using a Molecular Dynamics (MD) Simulation at temperature of 300 K for 10 nanoseconds. The results have shown that in general the conformation of T1 lipase enzyme in methanol is more dynamics as shown by the value of root mean square deviation (RMSD), root mean squared fluctuation (RMSF), and radius of gyration. The highest solvent accessible surface area (SASA) total was also found in methanol due to the contribution of non-polar amino acid in the interior of the protein. Analysis of MD simulation has also revealed that the enzyme structure tend to be more rigid in ethanol environment. The analysis of electrostatic interactions have shown that Glu359-Arg270 salt-bridge pair might hold the key of thermostability of T1 lipase enzyme as shown by its strong and stable binding in all three solvents.

PRODUCTION OF BIODIESEL FROM PALM OIL USING COCKLE SHELL WASTE AS HETEROGENEOUS CATALYST

In this study, production of biodiesel from palm oil using cockle shell wastes as catalyst was carried out using transesterification reaction. The objectives of this study are to analyze and characterize calcium oxide (CaO) from cockle shell wastes and to determine the catalytic activity of derived shell catalyst towards the percentage yield of biodiesel produced. The effect of methanol to oil ratio, reaction time and reaction temperature were investigated. The types of esters content in biodiesel and the functional group presence in catalyst were determined using FTIR and GC-MS analysis. The results showed that the optimum condition for cockle shell wastes achieved maximum yield of biodiesel (78.05%) is at reaction temperature 50°C within 1 hour with 9:1 methanol to oil ratio. Meanwhile for commercial CaO, the maximum yield is 73.95% at 60°C within 3 hours for 3:1 methanol to oil ratio. From the result obtained, this indicated that cockle shell wastes have potential to substitute commercial CaO as catalyst in transesterification reaction.

Catalytic optimization and physicochemical studies over Zn/Ca/Al2O3 catalyst for transesterification of low grade cooking oil

Recently, there has been an increasing interest in green and renewable fuels due to the worldwide concern of an environmental crisis. So, this study focused on the synthesis, optimization and characterization of series of heterostructure Zn/Ca/Al2O3 catalysts with different parameters to test their effectiveness towards biodiesel production. The physicochemical properties of the potential catalyst were determined by BET, FESEM and CO2-TPD. The activity of the catalyst in transesterification reaction was evaluated at reaction temperature of 65°C, 3h reaction time, 6% (w/w) catalyst concentration and 1:24M ratio of oil to methanol. The investigation of the synthesized Zn/Ca/Al2O3 catalyst showed that the calcination temperature, number of alumina coatings and dopant to base ratio have significant effects on the catalytic performance. These three critical parameters were investigated using response surface methodology (RSM) with Box Behnken design (BBD) to determine the optimum operating conditions for biodiesel production. From RSM study, the optimum conditions were 800°C calcination temperature, 3 times alumina beads coating and 10:90 dopant to base ratio which gave 97.80% biodiesel conversion. From the F-value and low p-value (<0.05) obtained showed that the model was significant for predicting the optimum biodiesel conversion. An experiment was conducted under the optimum conditions to confirm the agreement of the model prediction and the experimental results. The experimental value (97.64%) closely agreed with the predicted results from RSM and hence validated the findings of response surface optimization.

Acid Modified Jourdiqua Clay for Methanolysis of Castor Oil

Clay and clay minerals have very promising future in catalysis of chemical reactions. In this work Jourdiqua clay from north of Sudan was acid modified and used as heterogeneous catalyst in transesterification reaction of castor oil with methanol. The clay was modified with hydrochloric acid, HCl. at 30%, 40%, 50%, 60% and 70% weight concentration with respect to the clay, respectively. The raw and acid modified clay were characterized by Fourier transform infrared analysis (FTIR), field emission electron microscope (FESEM), back titration, TPD-NH3 technique and nitrogen adsorption desorption (BET) analysis, to determine the physico-chemical properties and the acidity of the raw and modified clay. The surface area and active sites of the modified clays were found to increase with the acid treatment. Transesterification of castor oil with methanol were done under the reaction condition of 9% w/w catalyst loading, methanol to oil molar ratio of 18:1, 3 h reaction time and the reaction temperature of 67°C. The biodiesel yield was monitored using nuclear magnetic resonance 1HNMR spectroscopy. The highest conversion observed is 83.86% achieved by 50% HCl/Clay.

Tetraethylammonium hydrogen carbonate: A cheap, efficient, and recyclable catalyst for transesterification reactions under solvent-free conditions

ABSTRACTTetraethylammonium hydrogen carbonate (TEAHC) was proven to be an efficient catalyst for transesterification reactions in the absence of solvent. The reaction between isopropenyl or ethyl acetate and an alcohol (not efficient in the absence of catalyst) was induced by the presence of TEAHC, which seems to assist the proton transfer from the alcohol to the ester, yielding the corresponding acetate in very good yields in the absence of any solvent. Moreover, the TEAHC can be recycled several times without significant loss in activity.

Preparation and characterization of highly active solid base catalyst from snail shell for biodiesel production

ABSTRACTSnail shell (SS), a good natural source of calcium carbonate, was tested as a catalyst for transesterification reaction. SS was calcined and modified with potassium hydroxide (KOH) to obtain a catalyst with high activity, and characterized by Fourier-transform infrared spectra, X-ray diffraction, scanning electron microscope with Energy Dispersive Spectroscopy (EDS) and thermal gravimetric analysis. Calcined SS and KOH impregnated SS (KOH/SS) were tested for their catalytic activity via transesterification process, and it was found that biodiesel yield had been increased from 90 to 96%. The optimum conditions for the highest yield were 6 wt.% catalyst loading, 65°C temperature, 9:1 methanol to oil molar ratio, and 3.5 h reaction time. The solid base catalyst from SS exhibits excellent catalytic activity and stability for the transesterification reaction, which suggests that this catalyst could potentially be used as a solid base catalyst for biodiesel production. To examine the reusability of the catalyst developed from SS, five transesterification reaction cycles were performed.

Influence of green catalyst on transesterification process using ultrasonic-assisted

Expansion of biodiesel production through transesterification reaction is restricted on the highly corrosive catalyst that generates environmental pollution. An exploration towards an environment-friendly and cleaner catalyst using biomass waste has become an attractive research in recent years. The aim of this study is to investigate empty fruit bunch doped with potassium hydroxide as a heterogeneous solid base catalyst for transesterification of rubber seed oil with methanol in ultrasonic batch system. Catalyst preparation was done using incipient wetness impregnation method. Synthesised catalyst named empty fruit bunch-potassium hydroxide was characterised by Fourier Transform Infrared, X-ray Diffraction and Brunauer–Emmett–Teller. Maximum free fatty acid reduction of 97.6% via esterification in mechanical stirring reactor was attained using 2.5 wt. % sulphuric acid and 12:1 methanol to oil molar ratio at 65 °C for 50 min. In the case of transesterification, saponification was formed under operating conditions of 15 wt. % of synthesised catalyst and 15:1 methanol to oil molar ratio at 40 °C for 30 min. This study indicated that empty fruit bunch-potassium hydroxide as the catalyst in transesterification reaction was ineffectiveness when assisted by ultrasonic.

ChemInform Abstract: Advances in Solid‐Catalytic and Non‐Catalytic Technologies for Biodiesel Production

AbstractReview: 207 refs.

One-pot synthesis of glycidol from glycerol and dimethyl carbonate over KF/sepiolite catalyst

Abundantly available natural material, sepiolite was used in combination with KF to develop a transesterification catalyst and used to synthesize glycidol from glycerol and dimethyl carbonate (DMC) in a one step reaction. The composition of the sepiolite determined by X-ray florescence (XRF) makes it a unique candidate for transesterification of glycerol as most of its components have previously been used either in combinations or singly as catalyst for transesterification reactions. Other characterizations of the developed 30%KF/sepiolite catalyst were done by XRD, BET, and FTIR. The optimum reaction conditions of the KF/sepiolite catalyst on transesterification of glycerol with DMC were obtained at 85°C reaction temperature, 2:1 DMC/glycerol, 4% by weight catalyst loading and 90min reaction time. The developed catalyst can be reused up to four cycles with a minimal reduction in its efficiency in transesterification activities.

Calcium/chitosan spheres as catalyst for biodiesel production

Chitosan, an abundant biopolymer extracted from crustacean shells, can be used as a structuring agent by the insertion of calcium oxide and used as a catalyst in transesterification reactions. These calcium-incorporated chitosan spheres were calcined in order to obtain a porous calcium catalyst without organic material. The materials were characterized using X-ray diffraction, thermogravimetric analysis, Fourier transform infrared and X-ray photoelectron spectroscopies, temperature-programmed desorption of CO2, scanning electron microscopy and specific surface area analysis. Afterwards the calcined calcium/chitosan spheres were used in the transesterification reaction of sunflower oil with methanol. The conversion of sunflower oil to methyl esters (YFAME), under optimized reaction conditions, which were determined by factorial experimental design (XMR, 1:9; XCAT, 3 wt%; time, 4 h; temperature, 60 °C; magnetic stirring, 1000 rpm), was 56.12 ± 0.32 wt%. These results show that chitosan can be used as a precursor for the formation of calcium/chitosan spheres, yielding a porous calcium oxide (with higher surface area) that can be used as an alkaline catalyst for biodiesel production. © 2014 Society of Chemical Industry

Advances in solid-catalytic and non-catalytic technologies for biodiesel production

The insecure supply of fossil fuel coerces the scientific society to keep a vision to boost investments in the renewable energy sector. Among the many renewable fuels currently available around the world, biodiesel offers an immediate impact in our energy. In fact, a huge interest in related research indicates a promising future for the biodiesel technology. Heterogeneous catalyzed production of biodiesel has emerged as a preferred route as it is environmentally benign needs no water washing and product separation is much easier. The number of well-defined catalyst complexes that are able to catalyze transesterification reactions efficiently has been significantly expanded in recent years. The activity of catalysts, specifically in application to solid acid/base catalyst in transesterification reaction depends on their structure, strength of basicity/acidity, surface area as well as the stability of catalyst. There are various process intensification technologies based on the use of alternate energy sources such as ultrasound and microwave. The latest advances in research and development related to biodiesel production is represented by non-catalytic supercritical method and focussed exclusively on these processes as forthcoming transesterification processes. The latest developments in this field featuring highly active catalyst complexes are outlined in this review. The knowledge of more extensive research on advances in biofuels will allow a deeper insight into the mechanism of these technologies toward meeting the critical energy challenges in future.

MoO3/SO4 2−-TiO2 catalyst for transesterification of dimethyl cabonate with phenol

A new MoO3/SO4 2−-TiO2 catalyst was prepared by a conventional impregnation of SO4 2−/TiO2 as carrier with an aqueous solution of ammonium molybdate and used for the synthesis of transesterification of dimethyl carbonate (DMC) with phenol. A series of MoO3/SO4 2−-TiO2 catalysts with different MoO3 loadings were investigated and characterized using X-ray diffraction (XRD), Fourier transform infrared spectrometer (FTIR), NH3-temperature programmed desorption (NH3-TPD) and X-ray photoelectron spectroscopy (XPS). The results show that MoO3 loading is related to the activity of transesterification reaction. With the increase of MoO3 loading, the activity of transesterification reaction increases. The sulfur species in the catalyst have an influence on the molybdenum species, and lead to an increase in the electropositive of molybdenum, which promotes the catalytic activity of MoO3/SO4 2−-TiO2. Among the series of catalysts prepared, MoO3/SO4 2−-TiO2 with 10% MoO3 and 823 K calcinated is found to be the most active catalyst for transesterification reaction. Under the reaction conditions of 453 K and 12 h, the conversion of DMC is 30.5 %, and the yields of MPC and DPC reach 21.2 % and 8.7 %, respectively.

Microbial biodiesel production by direct methanolysis of oleaginous biomass

Biodiesel is usually produced by the transesterification of vegetable oils and animal fats with methanol, catalyzed by strong acids or bases. This study introduces a novel biodiesel production method that features direct base-catalyzed methanolysis of the cellular biomass of oleaginous yeast Rhodosporidium toruloides Y4. NaOH was used as catalyst for transesterification reactions and the variables affecting the esterification level including catalyst concentration, reaction temperature, reaction time, solvent loading (methanol) and moisture content were investigated using the oleaginous yeast biomass. The most suitable pretreatment condition was found to be 4gL(-1) NaOH and 1:20 (w/v) dried biomass to methanol ratio for 10h at 50°C and under ambient pressure. Under these conditions, the fatty acid methyl ester (FAME) yield was 97.7%. Therefore, the novel method of direct base-catalyzed methanolysis of R. toruloides is a much simpler, less tedious and time-consuming, process than the conventional processes with higher FAME (biodiesel) conversion yield.

Sodium titanate as basic catalyst in transesterification reactions

Sodium titanate was synthesized by the sol–gel method and characterized using X-ray diffraction, thermogravimetry-mass spectrometry, atomic absorption spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis and nitrogen physisorption. The non-calcined material was active as a catalyst in transesterification reactions and showed high stability. An appreciable loss of activity on the fourth reuse was accompanied by the appearance of a new species of oxygen and segregated sodium, identified by X-ray photoelectron spectroscopy (XPS). The XPS spectrum showed that the basic nature of the framework oxygen was inferior to the original basicity, which explained the decline in catalytic activity.

Transesterifcation of Palm Olein Oil Using Na&lt;sub&gt;3&lt;/sub&gt;PO&lt;sub&gt;4&lt;/sub&gt; as Heterogeneous Catalyst

Fatty acid methyl ester (FAME) production from transesterification reaction of palm olein oil with methanol in the presence of Na3PO4 as heterogeneous catalyst was investigated. The effects of molar ratio of methanol to oil, amount of catalyst and reaction temperature on the yield of FAME were studied. The results showed that sodium phosphate can be used effectively as heterogeneous catalyst in transesterification reaction. The rate of reaction and yield of FAME depend on molar ratio of methanol to oil, amount of catalyst used and operating temperature. Molar ratio of methanol to oil of higher than 18:1 gives fastest rate of reaction and highest FAME content. Higher operating temperatures tend to accelerate the rate of reaction but reduces glycerol by-product quality. When large excess of methanol is used, the experimental results agrees with irreversible 1st order kinetic model and the activation energy is found to be 43.6 kJ/mol.

Electrogenerated N‐Heterocyclic Carbenes in the Room Temperature Parent Ionic Liquid as an Efficient Medium for Transesterification/Acylation Reactions

AbstractN‐Heterocyclic carbenes (NHCs), generated by electrochemical reduction under galvanostatic control of 1,3‐dialkylimidazolium‐based ionic liquids, were employed as catalysts in transesterification reactions in the parent, room temperature ionic liquids (RTILs) as solvents, without the utilisation of any volatile organic solvent or base. The reaction between isopropenyl or ethyl acetate and an alcohol (not efficient in the absence of catalyst) was induced by the presence of an electrogenerated NHC, which seems to assist the proton transfer from the alcohol to the ester, yielding the corresponding acetate. The reaction also proceeds with methyl nicotinate as starting ester and 2‐(diethylamino)ethanol or benzyl alcohol as alcohols and leads to the corresponding biologically active compounds, nicametate and benzyl nicotinate, in good yields. All products were isolated in good to excellent yields and complete recyclability of the ionic liquid as solvent has been demonstrated.

Waste capiz (Amusium cristatum) shell as a new heterogeneous catalyst for biodiesel production

The waste Capiz shell was utilized as raw material for catalyst production for biodiesel preparation. During calcination process, the calcium carbonate content in the waste capiz shell was converted to CaO. This calcium oxide was used as catalyst for transesterification reaction between palm oil and methanol to produce biodiesel. The biodiesel preparation was conducted under the following conditions: the mole ration between methanol and palm oil was 8:1, stirring speed was 700 rpm, and reaction temperature was 60 °C for 4, 5, and 6 h reaction time. The amount of catalyst was varied at 1, 2, 3, 4, and 5 wt %. The maximum yield of biodiesel was 93 ± 2.2%, obtained at 6 h of reaction time and 3 wt % of amount of catalyst. In order to examine the reusability of catalyst developed from waste of capiz (Amusium cristatum) shell, three transesterification reaction cycles were also performed.

Carbonate, acetate and phenolate phosphonium salts as catalysts in transesterification reactions for the synthesis of non-symmetric dialkyl carbonates

Methyl trioctylphosphonium methyl carbonate [P(8881)](+)[MeOCO(2)](-) was prepared by the alkylation of trioctyl phosphine with the non-toxic dimethyl carbonate. This salt was a convenient source to synthesize different ionic liquids where the methyl trioctylphosphonium cation was coupled to weakly basic anions such as bicarbonate, acetate, and phenolate. At 90-220 °C, all these compounds [P(8881)](+)X(-); X = MeOCO(2); HOCO(2); AcO; PhO were excellent organocatalysts for the transesterification of dimethyl and diethyl carbonate with primary and secondary alcohols, including benzyl alcohol, cyclopentanol, cyclohexanol, and the rather sterically hindered menthol. Conditions were optimized to operate with very low catalyst loadings up to 1 mol% and to obtain non-symmetric dialkyl carbonates (ROCO(2)R'; R = Me, Et) with selectivity up to 99% and isolated yields >90%. The catalytic performance of the investigated ionic liquids was discussed through a cooperative mechanism of simultaneous activation of both electrophilic and nucleophilic reactants.

Organic–inorganic hybrid porous aerogel: efficient catalyst in transesterification reactions

Hybrid silica-based porous aerogels containing propylsulfonic acid and methyl functionalities were prepared by co-condensation route from the corresponding mercaptopropyltriethoxysilane and methyltriethoxysilane precursors using aqueous ammonia as hydrolyzing agent in the absence of any organic templates. The hybrid aerogel was dried under supercritical CO2 and characterized by SEM, TEM, 13C CP-MAS NMR, 29Si MAS NMR, TG/DTA, and nitrogen adsorption/desorption analyses. The hybrid-silica aerogel containing propylsulfonic acid serves as an efficient heterogeneous acid catalyst in transesterification of fatty acid esters with methanol in a batch reactor.

The Effect of Using Catalyst in Transesterification Reaction on the Biofuels Quality from Sardine Flour Oil Waste

Process of the transesterification reaction of sardine flour oil waste with NaOH as base catalyst in producing biofuels was conducted. The research purpose has studied the influence of NaOH concentration in transesterification process and examinate its effect on the quality of biofuels production, conversion, and physic quality. The variables that analysed was the effect of NaOH concentration as catalyst (0.5%, 1.0%, 1.5%, and 2.0% from amount of oil and methanol) in the transesterification reaction step. The result showed that the increasing NaOH concentration (0.5% until 1.5%), enhanced the biofuel conversion (%). The highest conversion of biofuels was achieved by using 1.50% NaOH (w/w) with 45.34% biofuels conversion. The major component in the biofuels was methyl palmitate (20.31%). ASTM analysis data also supported that the biofuel product was in agreement with automotive diesel fuel specification. Keywords: catalyst, transesterification, biofuels, quality, wastes