Patent GB-692800-A (GB)
Title: Catalytic hydration of olefins
IPC: C07C29/04
Filed: 1950-08-15
Abstract: In the catalytic hydration of olefines by contacting the olefine and water simultaneously with a porous adsorptive hydration catalyst substantially free from sodium before the olefine and water are contacted with the catalyst the latter is submitted to a conditioning treatment with water or steam in the absence of olefine within the temperature range effective for catalytic hydration of olefines. Preferably the pressure of the conditioning treatment is within the hydrationrange.  Preferably the catalyst is continuously kept in contact with the water as the olefine is introduced.  Advantageously water is maintained in the liquid phase in contact with the catalyst at all times during the hydration, if necessary by pressure adjustments.  For vapour phase hydration temperatures of above about 300 DEG  F., e.g. 500-700 DEG  F., preferably 550-600 DEG  F., space velocities of 1-5 with an optimum at about 3 and mol. ratios of water to olefine of 5-40 : 1, preferably 7-15 : 1, with an optimum at 10 : 1, are used.  In liquid phase reactions temperatures of above 300 DEG F., e.g. 350-575 DEG  F., preferably 400-500 DEG  F., space velocities of 0.2-5.0, preferably 0.5-2.0, 0.5 being about optimum and mol. ratios of water to olefine of 0.5-20 : 1, preferably 1-5 : 1, are used.  In each case pressure may be 375-6000, e.g. 500-2500, preferably about 1500 p.s.i.g.  Catalysts specified include alumina, silica, zirconia and thoria and natural or synthetic composites of two or more of such oxides.  Silica-alumina composites are preferred, especially those containing a major proportion of silica and 1-35 per cent of alumina.  They may be prepared as in Specification 576,058, [Group III], and sodium should be substantially removed, e.g. by base exchange.  Olefines of 3-5 carbon atoms are mentioned.  A diagram is provided of suitable apparatus for the hydration of propylene and in examples propylene is hydrated in the presence of silica-alumina composites in (1)-(7), (11), (15) and (16); of silica (8); of activated alumina (9); of alumina gel (10); of activated montmorillonite (12); of silica-zirconia gel (14); and of silica-tungsten gel (17); and in (13) isobutylene; (18) penten-1; (19) mixed amylenes; and (20) hexene-1 are hydrated in the presence of silica-alumina composites.  Comparative experiments are also described in which sodium is not removed from the catalyst and in which the catalyst is not pretreated.  By preconditioning by-product formation, e.g. coke and polymers, is diminished.  Specification 622,937 also is referred to.ALSO:In the catalytic hydration of olefines by contacting the olefine and water simultaneously with a porous adsorptive hydration catalyst substantially free from sodium before the olefine and water are contacted with the catalyst the latter is conditioned with water or steam in the absence of olefine within the temperature range for catalytic hydration of olefins. Preferably the pressure of the conditioning treatment is within the hydration range.  For vapour phase hydration temperatures of above about 300 DEG F, e.g. 500-700 DEG F, preferably 550-600 DEG F, are used and for liquid phase reaction temperatures of above about 300 DEG F, e.g. 350-575 DEG F, preferably 400-500 DEG F, are used. Pressure may be 375-6000, e.g. 500-2500, preferably about 1500 p.s.i.g.  Catalysts specified include alumina, silica, zirconia and thoria and natural and synthetic composites of two or more such oxides. Silica-alumina composites are preferred especially those containing a major proportion of silica and 1-35 per cent of alumina. They may be made as in Specification 576,058.  In examples, propylene is hydrated in the presence of silica-alumina composites in 1-7, 11, 15 and 16, of silica 8, of activated alumina 9, of alumina gel 10, of activated montmorillonite 12, of silica-zirconia gel 14 and of silica-tungsten 12 and in 13 isobutylene, 18 pentene-1, 19 mixed amylenes and 20 hexene-1 are hydrated in the presence of silica-alumina composites. Comparative experiments are also described in which sodium is not removed from the catalyst and in which the catalyst is not pretreated.  By preconditioning by-product formation, e.g. coke and polymer is diminished.  Specification 662,937 also is referred to.