Transformation of organic compounds

摘要

The dehydration of normal alcohols to ethers and the hydration of olefins to alcohols is effected in the presence, as catalyst, of a crystalline, aluminosilicate, molecular sieve, having a sorption capacity of at least 4% by weight of n-butane at 760 mm. and 25 DEG C., and in the continuous or intermittent presence of carbon dioxide as an activator. The carbon dioxide, which may be formed in situ from carbon monoxide by reaction with water on the catalyst, is usually in an amount of 0.005-25% by weight of the catalyst in batch operations or 0.7-200% by weight per hour in continuous operations. The sieve may be of the A or X type, preferably an alkali or alkaline-earth metal alumino-silicate or may also contain cobalt, zinc, silver, nickel or ammonium introduced by base exchange. Dehydration of normal C3-C6 alcohols may be effected at 200-650 DEG F.; in an example 10.4g. of n-propyl alcohol are passed over a 13X molecular sieve with 4.4g. of carbon dioxide in one hour at 455 DEG F. to form din-propyl ether.ALSO:The following reactions are effected in the presence as catalyst of a crystalline aluminosilicate molecular sieve having a sorption capacity of at least 4% by weight of n-butane at 760 mm. and 25 DEG C. and in the continuous or intermittent presence of sufficient carbon dioxide to enhance to the activity of the catalyst: (a) cracking hydrocarbons to olefins; (b) dehydrating iso-alcohols to olefins; (c) isomerization of olefins, alkylcyclopentanes and terpenes; (d) polymerization of olefins and vinyl aromatic compounds; and (e) alkylation, dealkylation or disproportionation of aromatic hydrocarbons. Carbon dioxide may be formed in situ from carbon monoxide by reaction with water on the catalyst. The amount of carbon dioxide present may be 0.005-25% by weight of the catalyst or in continuous operations 0.7-200% by weight per hour. The molecular sieve may be of the A or X type and is preferably an alkali and/or alkaline earth metal aluminosilicate but may also contain cobalt, zinc, silver, nickel or ammonium introduced by base exchange. Cracking of C5-C30 paraffins to form olefins is preferably effected using a 13rA sodium, X molecular sieve at 550-1200 DEG F. and subatmospheric up to several hundred atmospheres pressure and an LHSV of 0.2-4. Dehydration of iso-alcohols containing 3-6 carbon atoms is effected at 200-650 DEG F. Double-bond isomerisation of olefins can be carried out at 30-900 DEG F.