Oxygenates, synthesis butanols

Isobutyl alcohol [78-83-1] forms a substantial fraction of the butanols produced by higher alcohol synthesis over modified copper—zinc oxide-based catalysts. Conceivably, separation of this alcohol and dehydration affords an alternative route to isobutjiene [115-11 -7] for methyl /-butyl ether [1624-04-4] (MTBE) production. MTBE is a rapidly growing constituent of reformulated gasoline, but its growth is likely to be limited by available suppHes of isobutylene. Thus higher alcohol synthesis provides a process capable of supplying all of the raw materials required for manufacture of this key fuel oxygenate (24) (see Ethers). 

In 1976 he was appointed to Associate Professor for Technical Chemistry at the University Hannover. His research group experimentally investigated the interrelation of adsorption, transfer processes and chemical reaction in bubble columns by means of various model reactions a) the formation of tertiary-butanol from isobutene in the presence of sulphuric acid as a catalyst b) the absorption and interphase mass transfer of CO2 in the presence and absence of the enzyme carboanhydrase c) chlorination of toluene d) Fischer-Tropsch synthesis. Based on these data, the processes were mathematically modelled Fluid dynamic properties in Fischer-Tropsch Slurry Reactors were evaluated and mass transfer limitation of the process was proved. In addition, the solubiHties of oxygen and CO2 in various aqueous solutions and those of chlorine in benzene and toluene were determined. Within the framework of development of a process for reconditioning of nuclear fuel wastes the kinetics of the denitration of efQuents with formic acid was investigated. 

Terminal alkenes can be selectively oxidized to aldehydes by reaction with oxygen, using a palladium-copper catalyst in tertiary butanol (equation 35)160. This reaction is contrary to the normal oxidation process which yields a ketone as the major product. The palladium(II) oxidation of terminal alkenes to give methyl ketones is known as the Wacker process. It is a very well established reaction in both laboratory and industrial synthesis161162. The Wacker oxidation of alkenes has been used in the key step in the synthesis of the male sex pheromone of Hylotrupes bajulus (equation 36)163. 

A homogeneous catalytic process, developed by Oxirane, uses a molybdenum catalyst that epoxidizes propylene by transferring an oxygen atom from tertiary butyl hydroperoxide. This is shown by 8.28. The hydroperoxide is obtained by the auto-oxidation of isobutane. The co-product of propylene oxide, /-butanol, finds use as an antiknock gasoline additive. It is also used in the synthesis of methyl /-butyl ether, another important gasoline additive. The over-... 

Functionalization of hydrocarbons from petroleum sources is mainly concerned with the introduction of oxygen into the hydrocarbon molecule. In general, two ways are open to achieve oxygen functionalization oxidation and carbonylation. Oxidation is commonly encountered in the synthesis of aromatic acids, acrolein, maleic anhydride, ethene oxide, propene oxide, and acetaldehyde. Hydroformylation (CO/H2) (older literature and the technical literature refer to the oxo reaction) is employed for the large-scale preparation of butanol, 2-ethylhexanol, and detergent alcohols. The main use of 2-ethylhexanol is in phthalate esters which are softeners in PVC. The catalysts applied are based on cobalt and rhodium. (For a general review see ref. 3.)... 

The dominant 0-addition to form 2-methyl-l-propanol occurs via a mechanistic path analogous to (24) as indicated by the 3C isotope experiments of Nunan et al. (ref. 57). This aldol path with oxygen retention reversal is further corroborated by the outcome of 2-propanol injection into the synthesis gas (ref. 49) which results in the dominance of 1-butanol in the C4 product,... 

By a similar mechanism to that proposed for the formation of ethyl ether by dehydration of ethanol, it is possible that the reaction occurs stepwise with the intermediate dehydration of one ethanol molecule to form ethylene which then reacts with another ethanol molecule to form butanol. It is thus possible that higher alcohols may be built up by the reaction of olefins with the lower alcohols. Mixed oxide type of catalysts are used in the process of a nature similar to those which have been found effective in alcohol synthesis from hydrogen and carbon monoxide. It should lie noted here that catalysts which promote the union of carbon atoms must be used, and since potassium oxide promoted catalysts composed of mixtures of zinc, copper, or chromium oxides have been found to be effective in the syuthesis of higher alcohols, such catalysts should be useful in promoting the addition of olefins to alcohols or other oxygenated organic molecules.77... 

An example is the synthesis of 2-butanol by the nickel-catalyzed hydrogenation of butanone. In this reaction the hydrogen molecule adds across the carbon—oxygen double bond in much the same way that it adds to a carbon—carbon double bond. 

TiCl4 in oxygen [11], hydrolysis of titanium alkoxides in different conditions [12], photo-assisted sol-gel method from titanium tetrabutoxide [13], hydrothermal oxidation of metallic titanium powder [14], hydrothermal hydrolysis of titanium tetraethoxide [15], oxysulfate [16,17] and tetrabutylammonium [18], solvothermal synthesis from titanium butoxide in 2-butanol [19], crystallization of amorphous Ti02 in hydrothermal condition [20], vapor hydrolysis of titanium tetraisopropox-ide [21], destabilization of titanium lactate [22], decomposition of titania-hydrate [23], epoxide sol-gel process to aerogel of Ti02 [24], hydrolysis of aqueous solution of TiCl4 in the presence of polyethyleneglycol [25], and so forth. 

Berridge, M. S., Cassidy, E. H., Terris, A. H., 1990. A routine, automated synthesis of oxygen-15-labeled butanol for positron tomography. J. Nucl. Med. 31 1727-1731. 

The bioalchols, such as bioethanol, biobutanol or bioglycerol can be converted to oxygenates fuel additives, acetals. The synthesis of acetal takes place by reacting one of these alcohols with and aldehyde, for example, n-butyraldehyde. Nowadays, aldehydes production takes place through hydroformylation reaction of alkenes, but other process such as bioalcohols oxidation can also be employed to produce aldehydes. Due to the origin of these bioalcohols, the production of the aldehydes by this new process is very attractive, therefore the butanol oxidation to butyraldehyde may be a way more consistent with the current environmental policies. 

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