| 摘要 |
Tertiary butanol is prepared by reacting isobutene and water at elevated pressure and at a temperature within the range of from 160 DEG to 220 DEG C. in the presence of an unsupported pelleted catalyst consisting of the blue oxide of tungsten having a formula approximating to W2O5 and prepared by reducing a hydrated tungsten trioxide or ammonium paratungstate at elevated temperatures. Secondary butanol is prepared in the same manner from butene-1 and/or butene-2 but at a temperature in the range of from 230 DEG to 270 DEG C. Water-to-olefine molecular ratios may vary from 1 : 1 up to as high as 20 : 1, the higher ratios being preferred. The process may be operated continuously, any unreacted olefine being recycled. A mixture of isobutene and either or both n-butenes and water may be passed over the catalyst at a temperature within the range of from 160 DEG to 220 DEG C., the resulting t-butanol separated from the reaction mixture and the residue, with more water, if necessary or desired, then passed over a second blue oxide of tungsten catalyst at a temperature in the higher range to form secondary butanol. Suitable catalysts are prepared by pelleting a mixture of powdered tungstic acid and 2 per cent graphite which is then reduced, for example, by treatment at an elevated temperature with hydrogen, carbon monoxide, mixtures containing these gases, or with a lower aliphatic alcohol, or it may be placed in the reaction vessel and treated at elevated temperature with the reactants; the tungstic acid may be replaced by ammonium para-tungstate. Examples describe the conversion of isobutene and butene-2 into the corresponding alcohols at 250 atmospheres pressure, the catalyst used being prepared by pelleting tungstic acid containing 2 per cent graphite and treating with ethanol for 3 hours at 250 DEG C., and then similarly treating with water. Specification 622,937 is referred to. According to the Provisional Specification the catalyst may be prepared by the reduction of WO3 containing 2 per cent of graphite.ALSO:Blue oxide of tungsten, for use as catalyst in the hydration of butenes to sec.- and tertiary-butanols, is prepared in unsupported pelleted form by reducing ammonium paratungstate or a hydrated tungsten trioxide, or WO3 according to the Provisional Specification, at elevated temperature. Hydrogen, carbon monoxide, or mixtures containing these gases, or lower aliphatic alcohols, may be used for the reduction; alternatively the pellets may be reduced in the reaction vessel by means of the reactants themselves. In an example, hydrated tungsten trioxide containing 2 per cent graphite is pelleted and then treated at 250 DEG C. with ethanol for 3 hours and then with water for three hours.
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