Showing papers on "Methanol published in 2006"

Formation of methyl formate and other organic species in the warm-up phase of hot molecular cores

Abstract: Aims. The production of saturated organic molecules in hot cores and corinos is not well understood. The standard approach is to assume that, as temperatures heat up during star formation, methanol and other species evaporate from grain surfaces and undergo a warm gas-phase chemistry at 100 K or greater to produce species such as methyl formate, dimethyl ether, and others. But a series of laboratory results shows that protonated ions, typical precursors to final products in ion-molecule schemes, tend to fragment upon dissociative recombination with electrons rather than just ejecting a hydrogen atom. Moreover, the specific proposed reaction to produce protonated methyl formate is now known not to occur at all. Methods. We utilize a gas-grain chemical network to probe the chemistry of the relatively ignored stage of hot core evolution during which the protostar switches on and the temperature of the surrounding gas and dust rises from 10 K to over 100 K. During this stage, surface chemistry involving heavy radicals becomes more important as surface hydrogen atoms tend to evaporate rather than react. Results. Our results show that complex species such as methyl formate, formic acid, and dimethyl ether can be produced in large abundance during the protostellar switch-on phase, but that both grain-surface and gas-phase processes help to produce most species. The longer the timescale for protostellar switch-on, the more important the surface processes.

Conversion of methanol into hydrocarbons over zeolite H-ZSM-5: ethene formation is mechanistically separated from the formation of higher alkenes.

Abstract: The widely debated reaction mechanism for the conversion of methanol to hydrocarbons over acidic zeolite H-ZSM-5 has been investigated using isotopic labeling. The mechanistic findings for H-ZSM-5 are clearly different from those previously described at a detailed level for H-β and H-SAPO-34 catalysts. On the basis of the current set of data, we can state that, for H-ZSM-5, ethene appears to be formed exclusively from the xylenes and trimethylbenzenes. Moreover, propene and higher alkenes are to a significant extent formed from alkene methylations and interconversions. This implies that ethene formation is mechanistically separated from the formation of higher alkenes, an insight of utmost importance for understanding and possibly controlling the ethene/propene selectivity in methanol-to-alkenes catalysis.

Solid Acid Catalysts for Biodiesel Production –-Towards Sustainable Energy

Abstract: The advantages of biodiesel as an alternative fuel and the problems involved in its manufacturing are outlined. The pros and cons of making biodiesel via fatty acid esterification using solid acid catalysts are examined. The main problem is finding a suitable catalyst that is active, selective, and stable under the process conditions. Various solid acids (zeolites, ion-exchange resins, and mixed metal oxides) are screened as catalysts in the esterification of dodecanoic acid with 2-ethylhexanol, 1-propanol, and methanol at 130–180 °C. The most promising candidate is found to be sulphated zirconia. The catalyst's stability towards thermal decomposition and leaching is tested and the effects of the surface composition and structure on the catalytic activity are discussed.

Formation of methyl formate and other organic species in the warm-up phase of hot molecular cores

Abstract: Aims: The production of saturated organic molecules in hot cores and corinos is not well understood. The standard approach is to assume that, as temperatures heat up during star formation, methanol and other species evaporate from grain surfaces and undergo a warm gas-phase chemistry at 100 K or greater to produce species such as methyl formate, dimethyl ether, and others. But a series of laboratory results shows that protonated ions, typical precursors to final products in ion-molecule schemes, tend to fragment upon dissociative recombination with electrons rather than just ejecting a hydrogen atom. Moreover, the specific proposed reaction to produce protonated methyl formate is now known not to occur at all. Methods: We utilize a gas-grain chemical network to probe the chemistry of the relatively ignored stage of hot core evolution during which the protostar switches on and the temperature of the surrounding gas and dust rises from 10 K to over 100 K. During this stage, surface chemistry involving heavy radicals becomes more important as surface hydrogen atoms tend to evaporate rather than react. Results: Our results show that complex species such as methyl formate, formic acid, and dimethyl ether can be produced in large abundance during the protostellar switch-on phase, but that both grain-surface and gas-phase processes help to produce most species. The longer the timescale for protostellar switch-on, the more important the surface processes.

Transesterification of soybean oil catalyzed by potassium loaded on alumina as a solid-base catalyst

Abstract: Biodiesel fuel, consisting of methyl esters of long chain fatty acids produced by transesterification of vegetable oils or animal fats with methanol, is a promising alternative diesel fuel regarding the limited resources of fossil fuels and the environmental concerns. In this work, an environmentally benign process for the transesterification of soybean oil to methyl esters using alumina loaded with potassium as a solid base catalyst in a heterogeneous manner was developed. The catalyst loaded KNO 3 of 35 wt.% on Al 2 O 3 , after being calcined at 773 K for 5 h, it was found to be the optimum catalyst, which can give the highest basicity and the best catalytic activity for this reaction. The effects of various reaction variables such as the catalyst loading, oil to methanol ratio, reaction time and temperature on the conversion of soybean oil were investigated. The catalysts were characterized by means of XRD, IR and Hammett titration method. The results indicated that K 2 O derived from KNO 3 at high temperature and that the Al–O–K groups were, probably, the main reasons for the catalytic activity towards the reaction. The catalyst activity was correlated closely with its basicity as determined by the Hammett method.

Calcined Mg–Al hydrotalcites as solid base catalysts for methanolysis of soybean oil

Abstract: Methyl ester of fatty acids, derived from vegetable oils or animal fats and known as biodiesel, is a promising alternative diesel fuel regarding the limited resources of fossil fuel and the environmental concerns. In this work, an environmentally benign process for the methanolysis of soybean oil to methyl esters using calcined Mg–Al hydrotalcites as solid base catalysts in a heterogeneous manner was developed. When the reaction was carried out at reflux of methanol, with a molar ratio of soybean oil to methanol of 15:1, a reaction time 9 h and a catalyst amount 7.5%, the oil conversion was 67%. The calcined hydrotalcite with an Mg/Al ratio of 3.0 derived from calcination at 773 K was found to be the optimum catalyst that can give the highest basicity and the best catalytic activity for this reaction. The catalysts were characterized with SEM, XRD, IR, DTA-TG and Hammett titration method. The activity of the catalysts for the methanolysis reaction was correlated closely with their basicity as determined by the Hammett method.

Comparison of two different processes to synthesize biodiesel by waste cooking oil

Abstract: The traditional acid and the new two-step catalyzed processes for synthesis of biodiesel expressed as fatty acid methyl ester (FAME) were comparatively studied to achieve an economic and practical method for utilization of waste cooking oil (WCO) from Chinese restaurants. WCO samples with the acid value of 75.92 ± 0.04 mgKOH/g mixed with methanol were catalyzed under 95 °C for various reaction time, followed by methanol recovery under vacuum (10 ± 1 mmHg) at 50 °C with a rotational evaporation. FAME analyzed by gas chromatography (GC) was obtained directly from sulfuric acid catalyzed reaction in the traditional acid method, whereas in the two-step method it was produced from ferric sulfate (2.0%) catalyzed reaction followed by alkali (1.0% potassium hydroxide) transesterification. The conversion of free fatty acids of WCO into FAME in the two-step method was 97.22% at the reaction time of 4 h, mole ratio of methanol to TG of 10:1, compared in the acid method with 90%, 10 h, and 20:1, respectively, showing much higher catalyzed activity of ferric sulfate. This new two-step process showed advantages of no acidic wastewater, high efficiency, low equipment cost, and easy recovery of catalyst compared with the limitations of acidic effluent, no reusable catalyst and high cost of equipment in the traditional acid process.

Acid-catalyzed production of biodiesel from waste frying oil

Abstract: The reaction kinetics of acid-catalyzed transesterification of waste frying oil in excess methanol to form fatty acid methyl esters (FAME), for possible use as biodiesel, was studied. Rate of mixing, feed composition (molar ratio oil:methanol:acid) and temperature were independent variables. There was no significant difference in the yield of FAME when the rate of mixing was in the turbulent range 100 to 600 rpm. The oil:methanol:acid molar ratios and the temperature were the most significant factors affecting the yield of FAME. At 70 °C with oil:methanol:acid molar ratios of 1:245:3.8, and at 80 °C with oil:methanol:acid molar ratios in the range 1:74:1.9–1:245:3.8, the transesterification was essentially a pseudo-first-order reaction as a result of the large excess of methanol which drove the reaction to completion (99±1% at 4 h). In the presence of the large excess of methanol, free fatty acids present in the waste oil were very rapidly converted to methyl esters in the first few minutes under the above conditions. Little or no monoglycerides were detected during the course of the reaction, and diglycerides present in the initial waste oil were rapidly converted to FAME.

Alumina-supported potassium iodide as a heterogeneous catalyst for biodiesel production from soybean oil

Abstract: Biodiesel fuel, a promising alternative diesel fuel produced by a catalytic transesterification of vegetable oils, has become more attractive recently because of its environmental concerns and the fact that it is made from renewable resources. In this work, the transesterification of soybean oil with methanol has been studied in a heterogeneous system, using alumina loaded with potassium iodide as a solid base catalyst. After loading KI of 35 wt.% on alumina followed by calcination at 773 K for 3 h, the catalyst gave the highest basicity and the best catalytic activity for this reaction. The catalysts were characterized by means of XRD, IR, SEM and the Hammett indicator method. Moreover, the dependence of the conversion of soybean oil on the reaction variables such as the catalyst loading, the molar ratio of methanol to oil and the reaction time was studied. The conversion of 96% was achieved under the optimum reaction conditions. Besides, a correlation of the catalyst activity for the transesterification reaction with its basicity was proposed.

Lipase-catalyzed transesterification of rapeseed oils for biodiesel production with a novel organic solvent as the reaction medium

Abstract: tert-Butanol, as a novel reaction medium, has been adopted for lipase-catalyzed transesterification of rapeseed oil for biodiesel production, with which both the negative effects caused by excessive methanol and by-product glycerol could be eliminated. Combined use of Lipozyme TL IM and Novozym 435 was proposed further to catalyze the methanolysis and the highest biodiesel yield of 95% could be achieved under the optimum conditions (tert-butanol/oil volume ratio 1:1; methanol/oil molar ratio 4:1; 3% Lipozyme TL IM and 1% Novozym 435 based on the oil weight; temperature 35 °C; 130 rpm, 12 h). There was no obvious loss in lipase activity even after being repeatedly used for 200 cycles with tert-butanol as the reaction medium. Furthermore, waste oil was also explored for biodiesel production and it has been found that lipase also showed good stability in this novel system.

The Hydrogenation/Transfer Hydrogenation Network: Asymmetric Hydrogenation of Ketones with Chiral η6-Arene/N-Tosylethylenediamine−Ruthenium(II) Catalysts

Abstract: Chiral η6-arene/N-tosylethylenediamine−Ru(II) complexes, known as excellent catalysts for asymmetric transfer hydrogenation of aromatic ketones in basic 2-propanol, can be used for asymmetric hydrogenation using H2 gas. Active catalysts are generated from RuCl[(S,S)-TsNCH(C6H5)CH(C6H5)NH2](η6-p-cymene) in methanol, but not 2-propanol, or by combination of Ru[(S,S)-TsNCH(C6H5)CH(C6H5)NH](η6-p-cymene) and CF3SO3H or other non-nucleophilic acids. This method allows, for the first time, asymmetric hydrogenation of simple ketones under acidic conditions. Hydrogenation of base-sensitive 4-chromanone and its derivatives with the S,S catalyst proceeds in methanol with a substrate-to-catalyst molar ratio of 1000−3000 (10 atm) to 7000 (100 atm), giving (S)-4-chromanols with 97% ee quantitatively. The reaction can be achieved even on a 2.4 kg scale. The mechanistic rationale for the catalytic efficiency is presented.

Room-Temperature Conversion of Soybean Oil and Poultry Fat to Biodiesel Catalyzed by Nanocrystalline Calcium Oxides

Abstract: A promising route for the production of biodiesel (fatty acid methyl esters, FAMES) via transesterification of soybean oil (SBO) and poultry fat with methanol in quantitative conversions at room temperature has been developed using nanocrystalline calcium oxides as catalysts. Under the same conditions, laboratory-grade CaO gave only 2% conversion in the case of SBO, and there was no observable reaction with poultry fat. The soybean oil/methanol ratio in our protocol is 1:27. With our most active catalyst, deactivation was observed after eight cycles with SBO and after three cycles with poultry fat. Deactivation may be associated with one or more of the following factors: the presence of organic impurities or adventitious moisture and enolate formation by the deprotonation of the carbon alpha to the carboxy group in the triglyceride or FAMES. The biodiesel from our protocol meets the ASTM D-874 standard for sulfated ash for both substrates.

Lipase catalyzed methanolysis to produce biodiesel: Optimization of the biodiesel production

Abstract: A lipase from Candida sp., suitable for transesterification of fats and oils to produce fatty acid methyl ester (FAME), was immobilized on a cheap cotton membrane, in this paper. The conversion ratio of salad oil to biodiesel could reach up to 96% with the optimal reaction conditions. Continuous reaction in a fixed bed reactor was also investigated. A three-step transesterification with methanol (methanolysis) of oil was conducted by using a series of nine columns packed with immobilized Candida sp. 99–125 lipase. As substrate of the first reaction step, plant or waste oil was used together with 1/3 molar equivalent of methanol against total fatty acids in the oil. Mixtures of the first- and second-step eluates and 1/3 molar equivalent of methanol were used for the second- and third-reaction steps. A hydrocyclone was used in order to on-line separate the by-product glycerol after every 1/3 molar equivalent of methanol was added. Petroleum ether was used as solvent (3/2, v/v of oil) and the pump was operated with a flow rate of 15 L/h giving an annual throughput of 100 t. The final conversion ratio of the FAME from plant oil and waste oil under the optimal condition was 90% and 92%, respectively. The life of the immobilized lipase was more than 10 days. This new technique has many strongpoints such as low pollution, environmentally friendly, and low energy costs.

Synthesis of Biodiesel from Soybean Oil using Heterogeneous KF/ZnO Catalyst

Abstract: Biodiesel was produced by transesterification of soybean oil with methanol using ZnO loaded with KF as a solid base catalyst. It was found that the catalyst with 15 wt.% KF loading and calcined at 873 K showed the optimum activity. XRD, IR and Hammett indicator method were employed for the catalyst characterization. The results showed the activity of the catalysts was correlated with their basicity. The influence of various reaction variables on the conversion was also discussed.

Continuous Production of Biodiesel via Transesterification from Vegetable Oils in Supercritical Methanol

Abstract: The continuous production of biodiesel (fatty acid methyl esters) by the transesterification reaction of coconut oil and palm kernel oil was studied in supercritical methanol without using any catalyst. Experiments were carried out in a tubular flow reactor, and reactions were studied at 270, 300, and 350 °C at a pressure of 10 and 19 MPa with various molar ratios of methanol-to-oils from 6 to 42. It was found that the best condition to produce methyl esters from coconut oil and palm kernel oil was at a reaction temperature of 350 °C, molar ratio of methanol-to-vegetable oil of 42, and space time 400 s. The % methyl ester conversions were 95 and 96 wt % for coconut oil and palm kernel oil, respectively. The regression models by the least-squares method were adequate to predict % methyl ester conversion with temperature, molar ratio of methanol-to-oil, and space time as the main effects. The produced methyl ester fuel properties met the specification of the ASTM biodiesel standards.

High Performance PtRuIr Catalysts Supported on Carbon Nanotubes for the Anodic Oxidation of Methanol

Abstract: We report the formation of a new PtRuIr catalyst using an organic colloid synthesis method, involving acetone as the solvent, ethylene glycol as the reducing agent, citrate as a complexing agent and stabilizer, and multiwall carbon nanotubes (CNT, diameter 8−10 nm) as the support. This catalyst has a very high real surface area and is highly active toward the oxidation of methanol, relevant to fuel cell applications. The Ir component appears to act as a promoter, and the splitting of the Pt(111) XRD feature into four peaks and the shift to larger d spacing reflect the high dispersion of the metallic components.

Effect of water on sulfuric acid catalyzed esterification

Abstract: This paper reports on an investigation into the impact of water on liquid-phase sulfuric acid catalyzed esterification of acetic acid with methanol at 60 °C. In order to diminish the effect of water on the catalysis as a result of the reverse reaction, initial reaction kinetics were measured using a low concentration of sulfuric acid (1 × 10 −3 M) and different initial water concentrations. It was found that the catalytic activity of sulfuric acid was strongly inhibited by water. The catalysts lost up to 90% activity as the amount of water present increased. The order of water effect on reaction rate was determined to be −0.83. The deactivating effect of water also manifested itself by changes in the activation energy and the pre-exponential kinetic factor. The decreased activity of the catalytic protons is suggested to be caused by preferential solvation of them by water over methanol. A proposed model successfully predicts esterification rate as reaction progresses. The results indicate that, as esterification progresses and byproduct water is produced, deactivation of the sulfuric acid catalyst occurs. Autocatalysis, however, was found to be hardly impacted by the presence of water, probably due to compensation effects of water on the catalytic activity of acetic acid, a weak acid.

Novel Nanocomposite Pt/RuO2⋅x H2O/Carbon Nanotube Catalysts for Direct Methanol Fuel Cells

Abstract: The perfect combination: RuO2⋅x H2O for donating and accepting protons and electrons and carbon nanotubes (CNTs) for compensating the loss of electron conductivity caused by the RuO2 coating, improving the electrode microstructure, and lowering the electrode resistance. The result: superb performance of the title catalyst for direct electrooxidation of methanol.

Simulation of heterogeneously MgO-catalyzed transesterification for fine-chemical and biodiesel industrial production

Abstract: A heterogeneous magnesium oxide catalyst is a good alternative for homogeneous catalysts for the transesterification of alkyl esters for the production of fine-chemicals as well as for the production of biodiesel. The transesterification of ethyl acetate with methanol was used as a model reaction to simulate fine-chemical production in a batch slurry reactor at industrial conditions. The transesterification of triolein with methanol to methyl oleate was chosen to simulate continuous production of biodiesel from rapeseed oil. A kinetic model based on a three-step ‘Eley–Rideal’ type of mechanism in the liquid phase was used in both process simulations. The transesterification reaction occurs between methanol adsorbed on a magnesium oxide free basic site and ethyl acetate or the glyceride from the liquid phase. Methanol adsorption is assumed to be rate-determining in both processes. Activity coefficients were required to account for the significant non-ideality of the reaction mixture in the simulations of both processes. The simulations indicate that a production of 500 tonnes methyl acetate per year can be reached at ambient temperature in a batch reactor of 10 m 3 containing 5 kg of MgO catalyst, and that a continuous production of 100,000 tonnes of biodiesel per year can be achieved at 323 K in a continuous stirred reactor of 25 m 3 containing 5700 kg of MgO catalyst. Although various assumptions and simplifications were made in these explorative simulations the assumptions concerning the reaction kinetics used, the results indicate that for both processes a heterogeneous magnesium oxide catalyst shows promising potential as a viable industrial scale alternative.

Kinetics of heterogeneously MgO-catalyzed transesterification

Abstract: The transesterification of ethyl acetate with methanol over magnesium oxide as solid base catalyst was investigated. Intrinsic kinetic data have been obtained in a perfectly mixed slurry batch reactor. The influence of the temperature (283–323 K) and the initial methanol to ethyl acetate molar ratio (M/E: from 0.1 to 10) was investigated over a broad ethyl acetate conversion range (1–95%). A kinetic model was developed based on a three-step ‘Eley–Rideal’ type of mechanism applied in liquid phase, describing the experimental data over the investigated range of experimental conditions. Transesterification reaction occurs between methanol adsorbed on a magnesium oxide free basic site and ethyl acetate from the liquid phase. Methanol adsorption is assumed to be rate-determining. Other models derived from other mechanisms were rejected based on statistical analysis, mechanistic considerations and physicochemical interpretation of the parameters. The calculation of activity coefficients accounting for non-ideality had to be incorporated in the parameter estimation procedure.