Patent GB-437188-A (GB)
Title: Improvements in or relating to the treatment of olefinic hydrocarbons
IPC: C07C2/18
Filed: 1934-04-13
Abstract: <PICT:0437188/IV/1> Olefines containing more than two carbon atoms are polymerized to produce products of the nature of gasoline, for instance, boiling from 38 to 204 DEG  C. by means of catalysts comprising a phosphoric acid and a solid adsorbent which mixture has been calcined at 180--300 DEG  C. for a sufficient time to remove largely the water present.  The catalyst mass may be made by mixing a phosphoric acid with inert siliceous material (such as kieselguhr, fuller's earth, Bentonite, montmorellonite and the material sold under the Registered Trade Mark "Sil-o-cel") and/or metal oxides or chlorides such as zinc, aluminium, and alkaline earth chlorides, and calcining the mixture at the temperature stated.  Organic materials such as cellulose, starch, sugars, glue, gelatin, flour, molasses, asphalts or tars may be incorporated in the catalyst mass so as to yield a residue of carbon in the finished catalyst; or the tarry matter deposited on the catalyst during use may be utilized in this manner by grinding and pelleting the catalyst and if desired submitting it to an activating treatment with nitrogen, steam and air to remove a portion of the carbonaceous matter and leave a porous residue.  In the apparatus shown, the olefine gas passes from a supply pipe 1 through a heater 3 and thence to a wash tower 6 in which it is treated with caustic soda solution to remove sulphuretted hydrogen, thence through a heater 23 to a column 26 or 34 containing for instance fuller's earth or similar clay to remove constituents that would produce resinous matter, then through a cooler 30 or 40 to remove any condensate, to a container 33.  The gas is then sent by a pump 45 through a heater 48 to catalytic chambers 53 and 70 in series, the first of which may be adapted to polymerize the more reactive ingredients such as isobutylene and the second to polymerize the butenes and propylene.  These chambers may also be connected in parallel for alternate use.  The products are liquefied in coolers 59, 76.  The condensates are stabilized as in usual practice by treating them after a preliminary heating in a heater 94 in a tower 99 containing for example a reboiling coil 100, the lowest boiling constituents being removed through a valve 102.  The catalyst and the pretreating material may be regenerated when necessary by means of heated air or steam or both which may be supplied from a heater 129. In examples, the catalyst is made from (1) phosphoric acid, zinc oxide, zinc chloride and aluminium hydrate; (2) phosphoric acid, magnesium chloride, alumina, magnesia, starch, and kieselguhr; (3) phosphoric acid and kieselguhr.ALSO:<PICT:0437188/III/1> Olefines containing more than two carbon atoms are polymerized to produce products of the nature of gasoline, for instance boiling from 38 to 204 DEG  C., by means of catalysts comprising a phosphoric acid and a solid adsorbent which mixture has been calcined at 180--300 DEG  C. for a sufficient time to remove largely the water present.  The catalyst mass may be made by mixing a phosphoric acid with inert siliceous material (such as kieselguhr, fuller's earth, bentonite, montmorellonite and the material sold under the Registered Trade Mark "Sil-o-cel") and/or metal oxides or chlorides such as zinc, aluminium, and alkaline earth oxides, and zinc and alkaline earth chlorides, and calcining the mixture at the temperature stated. Organic materials such as cellulose, starch, sugars, glue, gelatin, flour, molasses, asphalts or tars may be incorporated in the catalyst mass so as to yield a residue of carbon in the finished catalyst; or the tarry matter deposited on the catalyst during use may be utilized in this manner by grinding and pelleting the catalyst and if desired submitting it to an activating treatment with nitrogen steam and air to remove a portion of the carbonaceous matter and leave a porous residue.  In the apparatus shown, the olefine gas passes from a supply pipe 1 through a heater 3 and thence to a wash tower 6 in which it is treated with caustic soda solution to remove sulphuretted hydrogen, thence through a heater 23 to a column 26 or 34 containing for instance fuller's earth or similar clay to remove constituents that would produce resinous matter, then through a cooler 30 or 40 to remove any condensate to a container 33.  The gas is then sent by a pump 45 through a heater 48 to catalytic chambers 53 and 70 in series, the first of which may be adapted to polymerize the more reactive ingredients such as isobutylene and the second to polymerize the butenes and propylene.  These chambers may also be connected in parallel for alternate use.  The products are liquefied in coolers 59, 76.  The condensates are stabilized as in usual practice by treating them after a preliminary heating in a heater 94 in a tower 99 containing for example a reboiling coil 100, the lowest boiling constituents being removed through a valve 102.  The catalyst and the pretreating material may be regenerated when necessary by means of heated air or steam or both which may be supplied from a heater 129. In examples the catalyst is made from (1) phosphoric acid, zinc oxide, zinc chloride and aluminium hydrate; (2) phosphoric acid, magnesium chloride, alumina magnesia, starch, and kieselguhr; (3) phosphoric acid and kieselguhr.