Methanol alkaline catalyst-mixture

The refined oil is mixed with the methanol/alkaline catalyst-mixture, reacting at mild temperature and low pressure and left in a settler for phase separation by gravity. 

Low Hp/CCf ratios under more moderate temperatures and pressures, with copper ased methanol synthesis catalysts possibly alkalinized yield methanol-higher alcohol mixtures (4-6) with rather high contents (5-12 wt %) of other oxygenated molecules (ketones, esters) - (7>8). 

Alkaline earth metal oxides and hydroxides have also been tested in transesterification reactions. Ca(OH)2 did not show significant catalytic activity in the transesterification of rapeseed oil with methanol at conditions normally used to prepare biodiesel.Peterson et al. reported relative alcoholysis activities of a series of supported CaO catalysts under near reflux conditions of methanol-rapeseed oil mixtures at 6 1 molar ratios.Among the catalysts tested, the most active was CaO (9.2 wt% CaO) on MgO. For instance, in a 12 h reaction the total oil conversion using this catalyst was over 95%, similar to... 

There is some question as to whether acetic acid would be formed from the reaction in the presence of the more alkaline catalysts, since it has been claimed that by passing a mixture of carbon monoxide and methanol vapor over solid sodium methoxide under high pressure, methyl formate is formed 90h... 

The mixture is filtered off from the catalyst, made acidic with dilute hydrochloric acid, and the methanol is removed under vacuum. The remaining aqueous solution is made alkaline with solution of sodium hydroxide and extracted with ether. After drying and concentrating the ether extract, there is obtained 1 7 g 1 -isoprOpylamino-4,4boiling point164°Cto 165°C/0.05 mm. The hydrochloride melts at 230°C. 

Biodiesel is a mixture of methyl esters of fatty acids and is produced from vegetable oils by transesterification with methanol (Fig. 10.1). For every three moles of methyl esters one mole of glycerol is produced as a by-product, which is roughly 10 wt.% of the total product. Transesterification is usually catalyzed with base catalysts but there are also processes with acid catalysts. The base catalysts are the hydroxides and alkoxides of alkaline and alkaline earth metals. The acid catalysts are hydrochloride, sulfuric or sulfonic acid. Some metal-based catalysts can also be exploited, such as titanium alcoholates or oxides of tin, magnesium and zinc. All these catalyst acts as homogeneous catalysts and need to be removed from the product [16, 17]. The advantages of biodiesel as fuel are transportability, heat content (80% of diesel fuel), ready availability and renewability. The... 

A solution of 4-[2-(5-ethyl-2-pyridyl)ethoxy]nitrobenzene (60.0 g) in methanol (500 ml) was hydrogenated at room temperature under one atmospheric pressure in the presence of 10% Pd-C (50% wet, 6.0 g). The catalyst was removed by filtration and the filtrate was concentrated under reduced pressure. The residual oil was dissolved in acetone (500 ml)-methanol (200 ml). To the solution was added a 47% HBr aqueous solution (152 g). The mixture was cooled, to which was added dropwise a solution of NaN02 (17.3 g) in water (30 ml) at a temperature not higher than 5°C. The whole mixture was stirred at 5°C for 20 min, then methyl acrylate (112 g) was added thereto and the temperature was raised to 38°C. Cuprous oxide (2.0 g) was added to the mixture in small portions with vigorous stirring. The reaction mixture was stirred until nitrogen gas evolution ceased, and was concentrated under reduced pressure. The concentrate was made alkaline with concentrated aqueous ammonia, and extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried (MgS04) The solvent was evaporated off to leave methyl 2-bromo-3- 4-[2-(5-ethyl-2-pyridyl)ethoxy]phenyl propionate as a crude oil (74.09 g, 85.7%). 

Since biomass pyrolysis product mixtures are very complex and selectivities are low for specific products, considerable effort has been devoted to improving selectivities. Selectivities can sometimes be increased by addition of coreactants or catalysts, or by changing the pyrolysis conditions (cf. Nikitin et al, 1962). For example, the pyrolysis of maplewood impregnated with phosphoric acid increased the yield of methanol to 2.2 wt % of the wood as compared to 1.3 wt % obtained on dry distillation of the untreated wood. Addition of sodium carbonate to oak and maple increased the yield of methanol by 100 and 60%, respectively, compared to pyrolysis yields without sodium carbonate. Other weakly alkaline reagents exhibited a similar effect. Pyrolysis of wood in a stream of benzene, xylene, or kerosine increased the yields of acetic acid, aldehydes, and phenols and reduced the yield of tars. Optimization of pyrolysis conditions will be shown later to have large effects on product distributions and yields. 

In the proposed vapor phase processes for organic acid synthesis, carbon monoxide is passed with the vaporized aliphatic alcohol over catalysts similar in nature to those employed in the pressure synthesis of higher alcohols from hydrogen-carbon monoxide mixtures. Pressures on the order of 200 atmospheres are employed. Temperatures of about 200° to 300° C. are preferred but it is necessary to use somewhat higher ones in order to obtain sufficient reaction. Mixtures of the oxides of zinc and chromium or copper, promoted with alkali or alkaline earth oxides, are suitable catalysts for the formation of carbon-carbon linkages.97 Catalysts composed of an alkali, chromium, and molybdenum have been claimed for the synthesis of mixtures of higher alcohols, aldehydes, acids, esters, etc., from carbon monoxide and vaporized aliphatic alcohols as methanol, ethanol, etc., at temperatures of about 420° C. and a pressure of 200 atmospheres.98... 

In the polymerization of catechin by using laccase (ML) as catalyst, the reaction conditions were examined in detail [112], A mixture of acetone and acetate buffer (pH 5) was suitable for the efficient synthesis of soluble poly(catechin) with high molecular weight. The mixed ratio of acetone greatly affected the yield, molecular weight, and solubility of the polymer. The polymer synthesized in 20% acetone showed low solubility toward DMF, whereas the polymer obtained in the acetone content less than 5% was completely soluble in DMF. In the UV-Vis spectrum of poly(catechin) in methanol, a broad peak centered at 370 nm was observed. In alkaline solution, this peak was red-shifted and the peak intensity became larger than that in methanol. In the ESR spectrum of the enzymatically synthesized poly (catechin), a singlet peak at g= 1.982 was detected, whereas the catechin monomer possessed no ESR peak. 

Rutin is one of the most commonly found flavonol glycosides identified as vitamin P with quercetin and hesperidin. An oxidative polymerization of rutin using ML as catalyst was examined in a mixture of methanol and buffer to produce a flavonoid polymer [115]. Under selected conditions, the polymer with molecular weight of several thousands was obtained in good yields. The resulting polymer was readily soluble in water, DMF, and DMSO, although rutin monomer showed very low water solubility. UV measurement showed that the polymer had broad transition peaks around 255 and 350nm in water, which were red-shifted in an alkaline solution. ESR measurement showed the presence of a radical in the polymer. 

Oxidative rearrangements, via oxythallation, have been improved in yield and selectivity by the use of thallium(iii) nitrate supported on clay rather than in methanolic solution. Thus, cyclohexene gave an 85% yield of dimethoxymethyl-cyclopentane while 1-tetralone, which normally gives a complex mixture of products, gave a 1 1 mixture of methyl indane-l-carboxylate and 2-methoxytetralone. An efficient, large-scale procedure for the direct cis-dihydroxylation of olefins has been reported. The oxidant is t-butyl hydroperoxide and the catalyst osmium tetroxide, with the reaction conducted under alkaline conditions (E%N OH ), so facilitating a rapid turnover of catalyst via enhanced hydrolysis of the osmate esters. The method appears to be more advantageous for the more substituted olefins than the Hofmann and Miles procedure. 

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