Patent GB-473334-A (GB)
Title: Improvements in or relating to the manufacture and production of lubricating oils
IPC: C10G50/02
Filed: 1936-04-07
Abstract: In the reaction of aromatic hydrocarbons with halogenated aliphatic hydrocarbons in the presence of ordinary or activated aluminium or an aluminium halide, the separation of the catalyst from the crude product, or from the layers into which the crude product may separate, is effected by treating the crude product or the separated layers (a) at a raised temperature with ammonia, or (b) at a temperature not below about 200 DEG  C. with a substantially anhydrous halide, sulphate or phosphate of a metal of the first or second periodic group (including ammonium) or with an oxide or hydroxide of a metal of the second periodic group; the mixture is then filtered or decanted.  When treatment (a) is applied, the treatment may be begun at atmospheric temperature and may be effected either by passing ammonia into the material or by adding a solution of ammonia in a solvent such as benzene or toluene; the use of alcoholic ammonia is excluded, and the use of aqueous ammonia is not recommended.  Specified compounds for use in treatment (b) are ammonium sulphate, ammonium chloride, sodium sulphate, sodium chloride, potassium chloride, copper chlorides, copper sulphate, calcium chloride, calcium phosphate, strontium sulphate, calcium sulphate, calcium fluoride, barium hydroxide, and calcium oxide.  The process is particularly useful in the manufacture of lubricating oils and pourpoint depressants by condensing aromatic hydrocarbons with halogenated aliphatic hydrocarbons having a molecular weight of 200 or above.  When, in this application of the invention, the whole product is treated as described above, a coloured fluorescent lubricating oil is obtained; if the separated layers are treated, the upper layer yields a light-coloured lubricating oil and the lower layer yields a viscous liquid or resinous solid which can be added to other lubricants to impart fluorescence thereto; if the treated lower layer is too viscous to filter or decant, it may be extracted with a solvent after the treatment.  The reaction may be effected in the presence or absence of a diluent, which may be an excess of the aromatic hydrocarbon, and when a diluent is used the treatment described above may be combined with the removal of the diluent by distillation.  In the examples: (1) chlorinated paraffin wax and benzene are condensed in the presence of aluminium chloride, and the layers of the reaction product are separated and heated to 200 DEG C. with sodium chloride; (2) a lower layer obtained as in example 1 is heated to 280 DEG  C. with ammonium chloride or (example 3) zinc chloride; (4) a product obtained as in example 1 is heated to 300 DEG C. with calcium fluoride or (example 5) cupric sulphate, without preliminary separation of the layers; (6) chlorinated paraffin wax is condensed with benzene in the presence of aluminium chloride, and ammonia is passed into the product at a temperature below 50 DEG  C. but above atmospheric temperature; (7) a lower layer obtained as in example 1 is heated to 300 DEG  C. with potassium chloride or (example 8) sodium sulphate; (9) a chlorinated shale oil is condensed with benzene in the presence of aluminium chloride, and the product is treated with ammonia until heat is no longer evolved; (10) ethylene dichloride is condensed with benzene in the presence of aluminium chloride, and the product is treated with ammonia until heat is no longer evolved; the mixture is then filtered and distilled, dibenzyl and a residue of higher boiling point being obtained.  Specifications 349,071; 402,253, [Group III], and 416,379 are referred to.  The first Provisional Specification describes the treatment, with halides of metals of the first or second periodic group, of products obtained by condensing halogenated hydrocarbons with cyclic hydrocarbons in the presence of metal halides or of metals or activated metals; it refers also to Specification 415,065, [Group III].ALSO:In the reaction of aromatic hydrocarbons with halogenated aliphatic hydrocarbons in the presence of ordinary or activated aluminium or an aluminium halide, the separation of the catalyst from the crude product, or from the layers into which the crude product may separate, is effected by treating the crude product or the separated layers (a) at a raised temperature with ammonia, or (b) at a temperature not below about 200 DEG  C. with a substantially anhydrous halide, sulphate or phosphate of a metal of the first or second periodic group (including ammonium) or with an oxide or hydroxide of a metal of the second periodic group; the mixture is then filtered or decanted.  When treatment (a) is applied, the treatment may be begun at atmospheric temperature and may be effected either by passing ammonia into the material or by adding a solution of ammonia in a solvent such as benzene or toluene, the use of alcoholic ammonia is excluded, and the use of aqueous ammonia is not recommended.  Specified compounds for use in treatment (b) are ammonium sulphate, ammonium chloride, sodium sulphate, sodium chloride, potassium chloride, copper chlorides, copper sulphate, calcium chloride, calcium phosphate, strontium sulphate, calcium sulphate, calcium fluoride, barium hydroxide, and calcium oxide.  The process is particularly useful in the manufacture of lubricating oils and pour-point depressants by condensing aromatic hydrocarbons with halogenated aliphatic hydrocarbons having a molecular weight of 200 or above.  When, in this application of the invention, the whole product is treated as described above, a coloured fluorescent lubricating oil is obtained; if the separated layers are treated, the upper layer yields a light-coloured lubricating oil and the lower layer yields a viscous liquid or resinous solid which can be added to other lubricants to impart fluorescence thereto; if the treated lower layer is too viscous to filter or decant, it may be extracted with a solvent after the treatment.  The reaction may be effected in the presence or absence of a diluent which may be an excess of the aromatic hydrocarbon, and when a diluent is used the treatment described above may be combined with the removal of the diluent by distillation.  In the examples, (1) chlorinated paraffin wax and benzene are condensed in the presence of aluminium chloride, and the layers of the reaction product are separated and heated to 200 DEG C. with sodium chloride; (2) a lower layer obtained as in example 1 is heated to 280 DEG  C. with ammonium chloride or (example 3) zinc chloride; (4) a product obtained as in example 1 is heated to 300 DEG C. with calcium fluoride or (example 5) cupric sulphate, without preliminary separation of the layers; (6) chlorinated paraffin wax is condensed with benzene in the presence of aluminium chloride, and ammonia is passed into the product at a temperature below 50 DEG  C. but above atmospheric temperature; (7) a lower layer obtained as in example 1 is heated to 300 DEG  C. with potassium chloride or (example 8) sodium sulphate; (9) a chlorinated shale oil is condensed with benzene in the presence of aluminium chloride, and the product is treated with ammonia until heat is no longer evolved. Specifications 349,071, 402,253, and 416,379 are referred to.  The first Provisional Specification describes the treatment, with halides of metals of the first or second periodic group, of products obtained by condensing halogenated hydrocarbons with cyclic hydrocarbons in the presence of metal halides or of metals or activated metals; it refers also to Specification 415,065.