Patent GB-1049325-A (GB)
Title: Conducting chemical reactions by means of radiation
IPC: C07C4/14
Filed: 1963-06-19
Abstract: Isopropylbenzene is dealkylated by exposing an inorganic solid of high surface area to radiation including U.V. and visible, ceasing to irradiate, contacting the solid with isopropylbenzene and removing the reactant and product from the solid.  The solids have a surface area of at least 1 m2g-1 are microporous, i.e. pores of 3A to 100 and have a pore volume of 5 to 70%. The solids exemplified are oxides of Si, Al, Ca, Ba, Ni and Fe; gels obtained by drying hydrated oxides such as Al2O3, SiO2, TiO2, ZrO2, MgO and zinc aluminate; synthetic and natural zeolites including ion exchangers; siliceous earths and clays; ceramic material; silicates and carbons.  The ionizing radiation may be accelerated electrons, protons, neutrons, a  and b particles, deutrons, fission fragments, g - and X-rays, derived from such sources as natural radio-active materials, nuclear reactors, fission products, 60Co, 37Cs, 24Na, 56Mn, 72Gd, 140La, and devices for producing charged particles by acceleration.  The level of radiation may be 1 kev to 30 mev whilst the dose applied to the solid may be 0.0001 to 1000 megarads. Irradiation may be carried out any temperature provided the excited states of the solid are preserved, 100 DEG  to 300 DEG  C. being preferable, whilst a vacuum or inert atmosphere may be used. In a specific embodiment, silica-alumina is irradiated using a cobalt-60 source.  The process may also be used for alkylation, aromatization, cracking, dearomatization, desulphurization, isomerization, and polymerization.ALSO:Hydrazine made from ammonia by exposing an inorganic solid of high surface area to radiation including U.V. and visible, ceasing to irradiate, contacting the solid with ammonia and removing the reactant and product from the solid.  The solids have a surface area of at least 1 m.2g.-1 are microporous, i.e. pores of 3A to 100 and have a pore volume of 5 to 70%. The solids exemplified are oxides of Si, Al, Ca, Ba, Ni and Fe; gels obtained by drying hydrated oxides such as Al2O3, SiO2, TiO2, ZrO2, MgO and zinc aluminate; synthetic and natural zeolites including ion exchangers; siliceous earths and clays; ceramic material; silicates and carbons.  The ionizing radiation may be accelerated electrons, protons, neutrons, a - and b -particles, deutrons, fission fragments, g - and X-rays, derived from such sources as natural radio-active materials, nuclear reactors, fission products, 60Co, 37Cs, 24Na, 56Mn, 72Gd, 140La, and devices for producing charged particles by acceleration.  The level of radiation may be 1 kev to 30 mev whilst the dose applied to the solid may be 0.0001 to 1000 megarads. Irradiation may be carried out at any temperature provided the excited states of the solid are preserved, 100 DEG  to 300 DEG  C. being preferable, whilst a vacuum or inert atmosphere may be used.ALSO:Chemical reactions are carried out by exposing an inorganic solid of high surface area to radiation, ceasing to irradiate, contacting the solid with at least one chemical reactant, the reactant forming a product and removing the reactant and product from the solid.  The solids have a surface area of at least 1 m2/g, have pore radii of 3 to 100   and have a pore volume of 5 to 70%.  The solids exemplified are oxides of Si, Al, Ca, Ba, Ni and Fe; gels obtained by drying hydrated oxides such as Al2O3, SiO2, TiO2, ZrO2, MgO and zinc aluminate; synthetic and natural zeolites including ion exchangers; siliceous earths and clays; ceramic material; silicates and carbons.  Radiation may be high energy radiation, ionising radiation, U.-V. and visible radiation: accelerated electrons, protons, neutrons, a - and b -particles, deutrons, fission fragments, g - and X-rays (derived from such sources as natural radioactive materials, nuclear reactors, fission products, 60Co, 37Cs, 24Na, 56Mn, 72Gd, 140La, and devices for producing charged particles by acceleration are specified).  The level of radiation may be 1 kev to 30 mev whilst the dose applied to the solid may be 0.0001 to 1,000 megarads.  Irradiation may be carried out at any temperature provided the excited states of the solid are preserved, 100 to 300 DEG C being preferable, whilst a vacuum or inert atmosphere may be used.  In a specific embodiment silica-alumina is irradiated using a cobalt-60 source and used to dealkylate isopropylbenzene. The process may also be used to convert NH3 into N2H4, and for alkylation, aromatization, cracking, dearomatization, desulphurization, isomerization, and polymerization.