Patent GB-855091-A (GB)
Title: Partial oxydation of organic compounds
Inventor: FENSKE MERRELL ROBERT
IPC: C07C51/16
Filed: 1959-01-09
Abstract: A feed comprising an organic substance in the form of a gas or a liquid which vaporizes under the reaction conditions is partially oxidized by passing downwardly at elevated temperature through a reaction zone with an oxidizing gas whilst causing relatively cooler finely-divided solid particles to fall freely in said zone to prevent the temperature from rising (see Group III). Compounds which may be partially oxidized by this method are hydrocarbons (ethane, propane, butane, pentane, hexane, heptane, decane, cyclopentane, cyclohexane, cycloheptane, methyl cycloheptane, 2,2,4-trimethyl pentane, propylene, butylene, hexene, naphthenes, benzene, toluene, naphthalene) alcohols (C4-C10 alcohols, butanol-1, n-hexanol, octanol-1, tridecyl alcohol) ketones (C4-C10 ketones, heptanone-2), ethers, esters and amines.  In the example, a light virgin naphtha is partially oxidized at about 400 DEG C. to give a product comprising a hydrocarbon layer containing olefins, carbonyls and cyclic ethers, a water layer containing lower molecular weight carbonyls, alcohols and formaldehyde and non-condensible gases comprising carbon monoxide and dioxide and light hydrocarbons.  It is stated that with n-hexane, n-hexanol or cyclohexane as a reactant the product comprises cyclic ethers (tetrahydrofurans) and ethylene oxide derivatives thereof, olefinic compounds and carbonyl compounds (aldehydes and ketones). Suitable oxidizing gases are oxygen, air, enriched air and oxygen/steam.  The preferred temperature range is 250-700 DEG C.: the residence time in the reactor is preferably 0,25-10 seconds.  If desired the reaction may be further controlled by passing the mixture of solids and products to a zone in which the solids form a relatively dense bed: this may be achieved by passing the mixture into a solids recycle line the diameter of which (or of a part of which) is suitably dimensioned in relation to that of the reactor; a fluidized bed may thus be formed.ALSO:<PICT:0855091/III/1> A feed comprising an organic substance in the form of a gas or a liquid which vaporizes under the reaction conditions is passed downwardly through a reaction zone at an elevated temperature with an oxidising gas whilst preventing the temperature from rising by causing relatively cooler finely-divided solid particles to fall freely in said zone co-currently with said gases, said solids being distributed evenly throughout said reaction zone and being present in a concentration not sufficient to arrest the reaction.  The solids and product are withdrawn and separated: if desired the gases may be used before separation, with or without an additional gas, to lift the solids in a recycle circuit to a hopper above the reactor (Fig. 1): alternatively the gases may be separated and thereafter another gas used to recycle the solids (Fig. 2, not shown).  If desired, the mixture of solids and products may be passed to a zone in which the solids form a relatively dense bed whereby the reaction is further controlled: this may be achieved in the first embodiment mentioned above by providing a suitable ratio of diameters in the reactor and recycle line or by increasing the diameter of part of the recycle line so that a fluidised bed of the solid in the product gases is formed. Numerous organic compounds are specified as reactants including ketones, ethers, esters and amines as well as alcohols and hydrocarbons from which in an example, there are obtained cyclic ethers, olefinic compounds and carbonyl compounds (see Group IV(b)): oxidising gases may be oxygen, air, enriched air and oxygen and steam.  Suitable temperatures are 250-700 DEG C.; the residence time in the reaction zone is preferably 0.25-10 seconds. Specified cooling solids are sand, quartz, glass beads, spent clays, fused alumina and coke; catalytic components include silver, copper, platinum, chromium, iron, tungsten oxide and molybdenum oxide.  The particles usually have a size between 5 and 800 microns.  The apparatus illustrated in Fig. 1 comprises a reactor 1 into which the organic compound is fed through line 7 and the oxidising gas through lines 8, 9, 10.  The cooling solids are supplied from a fluidised bed maintained in hopper 2, through a slide valve 6 and over distributing grids 18 and the product and solids are withdrawn from the reactor and pass through riser 12 into a cyclone 13 from which solids are returned to the hopper and gases are discharged at 14.  To increase the cooling effect, the feed may be introduced as a cold liquid at a plurality of points in the reactor.