Patent GB-788883-A (GB)
Title: Hydration of olefins with ion exchange resin catalysts
IPC: B01J31/10
Filed: 1955-10-25
Abstract: Normal olefines having 2 to 4 carbon atoms are converted into oxygenated products by passing a feed mixture of water, at least partly in liquid phase, and the olefine at a temperature between 250 DEG  and 425 DEG  F. over a catalyst which comprises a synthetic organic cation exchange resin in its acid form which is stable and insoluble under the hydration conditions, or a derivative of such a resin in which a proportion of the hydrogen ions are replaced by metal ions.  The products of the reaction are the corresponding alcohols and ethers.  Suitable ionexchange resins are, for example, synthetic aryl resins having a hydrocarbon skeleton combined with strong mineral acid groups, a portion of which may be in the form of a metal salt.  Suitable resinous materials for the preparation of the catalyst are, for example, thermosetting resins such as the solid condensation products of formaldehyde with phenol; natural resin-like materials such as coal, wood or waste petroleum sludge; and suitably cross-linked solid polymers of vinyl aromatic compounds such as styrene or vinyl toluene, or cross-linked copolymers of the vinyl aromatic compounds with other monoethylenically unsaturated compounds such as isobutylene, acrylonitrile or its homologues, acrylamide or its homologues, and methyl acrylate or methacrylate or its higher alkyl homologues. The most suitable catalysts are prepared from resinous copolymers of styrene containing a minor amount of p-divinylbenzene.  Other monovinyl aromatic compounds such as p-methyl styrene, p-ethyl styrene, dimethyl styrenes, p-chloro styrene, dichloro styrene and vinyl naphthalene may be used instead of styrene and other polyvinyl aryl compounds, such as divinyl toluene, divinyl xylene, divinyl ethyl benzene and divinyl chlorobenzene, may be used as cross-linking agents instead of divinyl benzene.  Other cross-linked polystyrenetype materials suitable for the preparation of catalyst are solid polymers containing 40 to 70 per cent styrene, 4 to 25 per cent divinyl benzene and 20 to 50 per cent isobutylene and those in which the divinyl benzene is replaced by butadiene or isoprene.  The polymers are sulphonated or phosphonated to introduce 0.25 to 3 inorganic acid radicals per benzene nucleus to convert them into the desired cation-exchange resins.  These resins may be further modified by replacing 5 to 95 per cent of their hydrogen ions with metal ions by impregnating the resin with an aqueous or acidic solution of a salt of the desired metal and washing off the free acid produced.  Suitable metals are, for example, copper, silver, iron, cobalt, nickel, chromium, molybdenum, tungsten, uranium, zinc, calcium, strontium, barium, radium, tin, titanium, manganese, cadmium, beryllium, magnesium, aluminium, lithium, lanthanum, platinum, palladium and vanadium.  In the examples: (a) a mixture of propylene and water is passed over sulphonated styrene-divinyl benzene copolymers to give a mixture of propyl alcohol and diisopropyl ether; (b) a mixture of ethylene and water is passed over Dowex SOX8 (a sulphonated resinous copolymer of styrene and divinyl benzene) to give ethyl alcohol; (c) a mixture of propylene and water is passed over various sulphonated polystyrene resins containing divinyl benzene as cross-linking agent to give mixtures of propyl alcohol and dipropyl ether; (d) a mixture of propylene and water is passed over a phosphoric hydrogen ion-exchange resin to give a mixture of isopropyl alcohol and diisopropyl ether; (e) a mixture of propylene and water is passed over a copper-modified sulphonated copolymer of styrene and divinylbenzene to give a mixture of isopropyl alcohol and diisopropyl ether; and details are given of the preparation of sulphonated copolymers of styrene and divinyl benzene modified by silver, tin, zinc, copper, cobalt, manganese, lithium, lanthanum and vanadium which may be used for the hydration of the olefines.ALSO:Catalysts for use in the hydration of olefines comprise synthetic organic cation exchange resins which are in the acid form or derivatives of such resins in which some of the hydrogen ions are replaced by metal ions.  Suitable resinous materials for use in the preparation of the catalysts include thermosetting resins such as coal, wood or waste petroleum sludge; cross-linked solid polymers of vinyl aromatic compounds such as styrene or vinyl toluene, or cross-linked copolymers of the vinyl aromatic compounds with other monoethylenically unsaturated compounds such as isobutylene, acrylonitrile or its homologues, acrylamide or its homologues and methyl acrylate or methacrylate or its higher alkyl homologues.  The most suitable catalysts are prepared from resinous copolymers of styrene containing a minor amount of p-divinylbenzene.  Alternatively other monovinyl compounds such as p-methylstyrene, p-ethylstyrene, dimethyl styrenes, p-chlorostyrene, dichlorostyrenes and vinyl naphthalene may be used instead of styrene and other cross-linking agents such as divinyl toluene, divinyl xylene, divinyl ethyl benzene, divinyl chlorobenzene and divinyl ethers may be used instead of p-divinyl benzene.  Other suitable cross-linked polystyrene type materials which are suitable are the copolymers of 40-70 per cent styrene, 20-50 per cent isobutylene and 4 to 25 per cent divinyl benzene; the divinyl benzene may be replaced by butadiene or isoprene and the resulting copolymer cross-linked or vulcanized after compounding with sulphur.  To convert these materials to the required cation-exchange resins they are sulphonated or phosphonated so that 0.25 to 3 inorganic acid radicals are introduced for each benzene nucleus.  These hydrogen-ion exchange resins may be further modified by replacing 5 to 95 per cent of their hydrogen ions with metal ions. Suitable metals are, for example, copper, silver, iron, cobalt, nickel, chromium, molybdenum, tungsten, uranium, zinc, calcium, strontium, barium, radium, tin, titanium, manganese, cadmium, beryllium, magnesium, aluminium, lithium, lanthanum, platinum, palladium and vanadium. With some metals, such as copper, part or all of the metal may advantageously be present as a free metal deposit rather than in ion form.