Patent GB-863539-A (GB)
Title: Phosphoric acid catalyst and a process for the conversion of organic compounds therewith
IPC: C07C37/14
Filed: 1959-10-12
Abstract: The polymerisation of olefines (including cyclic olefines) and the alkylation of organic compounds having a replacable hydrogen atom on a cyclic nucleus are effected in presence of a phosphoric acid/siliceous material catalyst (see Group III) the constituents of which are mixed in specified proportions, shaped and then calcined at 460-760 DEG C.; such cyclic compounds include hydrocarbons, phenols (and salts), amines, halides, ketones and carboxylic acid salts. Specified compounds are benzene, toluene, o-, m- and p-xylenes, ethylbenzene, o-, m- and p-diethylbenzenes, 1:2:3-, 1:2:4-and 1:3:5-trimetheylbenzenes, o- and p-ethyltoluenes, n- and iso-propylbenzenes, hexyl, heptyl, octyl and nonyl-benzenes and -toluenes, decylbenzene, dodecylbenzene, styrene, vinyltoluene, alkylbenzene, di- and tri-phenylmethene, fluorene, stilbene, naphthalene, anthracene, phenanthrene, chrysene, rubrene, indene, tetralin, indane, pyridene, furan, thiophene pyrrole, pyrazole, indole, carbazole, phenol, catechol, resorcinol, pyragallol, aniline, chloro- and bromo-benzene and o-, m- and p-toludines.  Specified olefines for polymerisation or use as alkylating agents are ethylene, propylene, 1- and 2-butenes, isobutylenes, pentenes, hexenes, 1:3- buta-, -penta- and -hexa-dienes, cyclopentene, cyclohexene, methylcyclopentene, methylcyclohexene and bicyclo [2.2.1]-2-heptene, and other alkylating agents are alkyl chlorides, bromides or iodides containing at least 2 carbon atoms per molecule, including ethyl, n-propyl, isopropyl, n-, iso- and t-butyl, amyl and hexyl chlorides and the corresponding bromides and iodides.  The olefines need not be pure and refinery gases containing minor amounts of gaseous olefines can be used as feed for either alkylation or polymerisation. Examples describe the production of ethylbenzene from ethylene and benzene.ALSO:A catalyst is prepared by heating, until in a semi-solid mouldable state, an intimate mixture of a phosphoric acid with a finely-divided solid siliceous material, thereafter transforming the mixture into shaped particles and calcining the latter at 460-760 DEG C.  The mixture has a phosphorus content (determined as P2O5) of 2.37 to 7.65 parts by weight per part of the siliceous material; the latter is preferably a diatomaceous earth but may also be artificially prepared porous silica or aluminium silicates including fuller's earths and clays such as bentonite and montmorillonite, as well as acid treated clays.  The phosphoric acids used include ortho-, pyro-, tri-, tetra-, and hexaneta-phosphoric acids and mixtures thereof.  The catalyst may be used, e.g., in the alkylation of aromatic compounds and the polymerization of olefins. Tetraphosphoric acid may be made by dehydration by heating of the ortho- or pyroacids or by adding P2O5 to these acids.  In the latter case, P2O5 is added gradually until it constitutes 520% by weight of the total water present; or standing crystal of tetraphosphoric acid, which melt at 34 DEG  C. and have a S.G. of 1.1886 at 15 DEG C., separate.  "Polyphosphoric acid" is formed by heating the ortho- or pyro-acids (or their mixture) in, e.g., carbon-lined trays heated by means such as flue gases to give a product of 79-85% P2O5; such a product of 84% (or 79.5%) P2O5\t contained 5% (24.5%) ortho- 11% (45.2%) pyro-, 57% (26.0%) tri-, 17% (0%) hexaneta-and 10% (4.3%) unidentified phosphoric acids.