Patent GB-721272-A (GB)
Title: Improvements in and relating to the production of organic oxygen-containing compounds
Inventor: TAYLOR ARTHUR WILLIAM CHARLES
IPC: C07C27/22
Filed: 1950-09-05
Abstract: A process for the conversion to oxygen-containing organic compounds of olefines by means of CO and H2 in the liquid phase under elevated temperature and pressure in the presence as catalyst of cobalt or a cobalt compound in which subsequently to the conversion the cobalt dissolved in the liquid product is precipitated as metallic cobalt by reducing the partial pressure of CO over the liquid and separated therefrom on a magnetic element or elements is characterised in that the metallic cobalt disposed on the magnetic element or elements is subsequently converted into active catalytic form suitable for re-use in the main conversion by bringing into contact with it, while disposed on the said element or elements, a substantially single phase comprising a solution of CO, or of CO and H2, in a liquid under conditions of elevated temperature and pressure, whereby a solution of cobalt carbonyl or/and cobalt hydrocarbonyl is formed. The liquid used in the solution of CO may be the olefine to be treated or when gaseous olefines, e.g. ethylene and propylene, are to be treated, may be an inert medium.  Preferably the dissolving agent is completely single phase.  The partial pressure may be lowered by the addition of H2.  In an illustration two similar vessels, preferably copper lined, or of stainless steel, each have a solution zone which is preferably packed, e.g. with grid packing, especially of egg-crate type, and a separation zone, preferably comprising a number of permanent magnets. The magnets may be in a series of trays or frames arranged so that the number of magnets per tray or frame increases progressively in the direction of liquid flow or the field strength may be increased by using progressively stronger magnets.  Strings of cylindrical magnets threaded on a non-magnetic rod may be used, each magnet being separated from its neighbours by a cylinder of non-magnetic material. Alternatively the magnetic filters of Specification 527,771, [Group II], may be used.  One of the vessels is used for stripping the liquid product whilst the other is used for the preparation of catalyst solutions.  Precipitation is effected with H2 and the CO and H2 mixture thus obtained is used in the conversion.  At the commencement of cobalt regeneration it is desirable that the CO/H2 ratio should be 1/1 , afterwards the proportion of CO is increased. Carbonylation may be effected at 100-180 DEG  C. and 150-300, preferably at least 200, atmospheres gauge.  Regeneration is preferably effected at 140-160 DEG  C. and 150-300 atmospheres gauge. The process is especially of value when soluble organic cobalt compounds are used, e.g. the acetate, naphthenate and hexoate. Preferably the solution of CO in the liquid contains a restricted amount of CO generally less than that required to saturate the liquid when regeneration is effected at 250 atmospheres gauge and such solutions may be obtained by mixing saturated or concentrated solutions with dilute solutions or with liquid containing no CO. This may be effected by introducing more liquid at a point of entry below the point of entry of CO to the solution zone. Specified olefines for carbonylation are di-isobutene, ethylene, propene, cyclohexene and cracked wax olefines. Regenerating-liquids specified are di-isobutene, iso-octane, nonanol, dinonyl ether and oxo synthesis residues from the hydrogenation stage.  Preferably inactive regenerating liquids are used which boil at N.T.P. at at least 50 DEG C. above or below the alcohol product.  When an olefine is used as regenerating liquid it should have a carbonylation activity of similar order to the olefine of the main process and its product should preferably boil at N.T.P. at least 50 DEG  C. above or below the main alcohol product. In an example, reduced cobalt metal on magnets of a magnetic separator is treated at 250 atmospheres gauge and 140 DEG  C. with di-isobutene containing CO to provide a solution of cobalt carbonyl.  Preferably the partial pressure of CO used in the regeneration step should be at least 50 atmospheres gauge. Specifications 659,712 and 672,880 are also referred to.ALSO:A process for the conversion to oxygen-containing organic compounds of olefines by means of CO and H2 in the liquid phase under elevated temperature and pressure in the presence as catalyst of cobalt or a cobalt compound in which subsequently to the conversion the cobalt dissolved in the liquid product is precipitated as metallic cobalt by reducing the partial pressure of CO on the liquid and separated therefrom on a magnetic element or elements is characterized in that the metallic cobalt disposed on the element or elements is subsequently converted into active catalytic form suitable for re-use in the main conversion by bringing into contact with it, while disposed on the element or elements, a substantially single phase comprising a a solution of CO, or of CO and H2, in a liquid under conditions of elevated temperature and pressure, whereby a solution of cobalt carbonyl or/and cobalt hydrocarbonyl is formed.  The liquid used in the solution of CO may be the olefine to be treated or when gaseous olefines e.g. ethylene and propylene, are to be treated may be an inert medium.  Preferably the dissolving agent is completely single phase.  The partial pressure may be lowered by the addition of H2.  In an illustration two similar vessels, preferably copper lined, or of stainless steel, each have a solution zone which is preferably packed e.g. with grid packing, especially of egg-crate type, and a separation zone preferably comprising a number of permanent magnets. The magnets may be in a series of trays or frames arranged so that the number of magnets per tray or frame increases progressively in the direction of liquid flow or the field strength may be increased by using progressively stronger magnets.  Strings of cylindrical magnets threaded on a non-magnetic rod may be used each magnet being separated from its neighbours by a cylinder of non-magnetic material. Alternatively the magnetic filters of Specification 527,771, [Group II], may be used.  One of the vessels is used for stripping the liquid product whilst the other is used for the preparation of catalyst solutions.  Precipitation is effected with H2 and the CO and H2 mixture thus obtained is used in the conversion.  At the commencement of cobalt regeneration it is desirable that the CO/H2 ratio should be 1/1, afterwards the proportion of CO is increased. Carbonylation may be effected at 100-180 DEG C. and 150-300, preferably at least 200, atmospheres gauge.  Regeneration is preferably effected at 140 -160 DEG C. and 150-300 atmospheres gauge. The process is especially of value when soluble organic cobalt compounds are used e.g. the acetate, naphthenate and hexoate. Preferably the solution of CO in the liquid contains a restricted amount of CO generally less than that required to saturate the liquid when regeneration is effected at 250 atmospheres gauge and such solutions may be obtained by mixing saturated or concentrated solutions with dilute solutions or solutions containing no CO.  This may be effected by introducing more liquid at a point of entry below the point of entry of CO to the solution zone.  Specified olefines for carbonylation are di-isobutene, ethylene, propylene, cyclohexene and craked wax olefines.  Regenerating liquids specified are di-isobutene, iso-octane, nonanol, dinonyl ether and other synthetic residues from the hydrogeneration stage.  Preferably inactive regenerating liquids are used which boil at N.T.P. at least 50 DEG C. above or below the alcohol product.  When an olefine is used as regenerating liquid it should have a carbonylation activity of similar order to the olefine of the main process and its product should preferably boil at N.T.P. at least 50 DEG C. above or below the main alcohol product.  In an example reduced cobalt metal on magnets of a magnetic separator is treated at 250 atmospheres gauge and 140 DEG C. with the di-isobutene containing CO to provide a solution of cobalt carbonyl.  Preferably the partial pressure of CO used in the regeneration stage should be at least 50 atmospheres gauge.  Specifications 659,712 and 672,880, [both in Group IV(b)], also are referred to.