Patent GB-472898-A (GB)
Title: Improvements in the treatment of hydrocarbons with chromyl chloride to produce oxidation, chlorination and polymerisation products of hydrocarbons
IPC: C10G17/09
Filed: 1936-03-26
Abstract: In the production of oxidation, chlorination, and polymerization products of hydrocarbons by treatment of hydrocarbon oils with chromyl chloride, in complete or almost complete absence of non-hydrocarbon liquids, the chromyl chloride is used as vapour, usually with a carrier gas, e.g. air, nitrogen, carbon dioxide.  A catalyst, e.g. an acid, a peracid, a metal oxide, or hydrogen peroxide, may be present, the oil may be in liquid or vapour form, the temperature may be elevated or reduced, and solid naphthenic hydrocarbons such as naphthalene or anthracene may be present.  In an example, 100 kg. of gas oil is treated at 30 DEG  F. with chromyl chloride vapour carried by carbon dioxide until 20 kg. of chloride is absorbed.  The precipitate is filtered off and decomposed by digestion with ether; aldehydes and ketones are precipitated by sodium bisulphite, acids are isolated by dilute caustic soda, and the ethereal solution is distilled to obtain ether and chlorinated hydrocarbons as distillates and resinous polymerized hydrocarbons as still residue.  The filtrate on distillation yields unaltered gas oil and a residue of polymerized hydrocarbons.  The decomposition of the precipitate may also be effected by heating, or by treatment with water, alcohols, acid, or caustic alkali.ALSO:In the production of oxidation, chlorination and polymerization products of hydrocarbons by treatment of hydrocarbon oils with chromyl chloride, in complete or almost complete absence of non-hydrocarbon liquids, the chromyl chloride is used as vapour, usually with a carrier gas, e.g. air, nitrogen, carbon dioxide.  A catalyst e.g. an acid, a peracid, a metal oxide, or hydrogen peroxide, may be present, the oil may be in liquid or vapour form, the temperature may be elevated or reduced, and solid naphthenic hydrocarbons such as naphthalene or anthracene may be present.  In examples: (1) 100 kg. of raffinate, from the extraction of dewaxed Persian lubricating - oil with liquid sulphur dioxide and benzol, is treated at 175 DEG  F. with chromyl chloride vapour carried by carbon dioxide until 8 kg. of chloride is absorbed. The 40 kg. of black precipitate is filtered off and decomposed by digestion with ether; aldehydes and ketones are precipitated by sodium bisulphite acids are isolated by dilute sodium hydrate, and viscous brown polymerization products suitable as pour - point depressants are obtained by distilling the residual ether solution. Alternatively the precipitate may be decomposed by heating, or by treating with water, alcohols, caustic alkali, or acid.  The filtrate, after boiling with sodium hydroxide solution to remove inorganic compounds, is lighter coloured than the initial raffinate, but is otherwise little changed; (2) 100 kg. of gas oil is treated at 30 DEG  F. until 20 kg. of chromyl chloride is absorbed.  The 88 kg. of precipitate is filtered off and treated as in the previous example; there are obtained 56 kg. of aldehydes and ketones, 4,5 kg. of organic acids, and after removing the ether a distillate of 3 kg. of chlorinated hydrocarbons and a still residue of resinous polymerized hydrocarbons.  The 32 kg. of filtrate on distillation yields unaltered gas oil as distillate and 2 kg. of polymerized hydrocarbons as still residue.