Patent GB-447778-A (GB)
Title: A process for the production of valuable viscous liquids
IPC: C07C1/26
Filed: 1934-12-01
Abstract: Viscous liquid products are obtained by treating chlorinated hydrocarbons containing at least ten carbon atoms with aromatic hydrocarbons in the presence of metallic aluminium (as distinct from activated aluminium), and separating the liquid product from the reaction sludge.  The reaction may be effected at atmospheric or raised temperature in the presence or absence of a non-aromatic hydrocarbon diluent.  A small proportion of iodine may be added, to start the reaction.  The separated liquid product may be refined by washing with water and/or dilute acid and/or dilute alkali, followed if desired by treatment with an adsorbent such as a bleaching earth; the diluent, if used, is then removed by distillation and the product is optionally refined further, as by vacuum distillation.  The reaction sludge may be used as a catalyst in the reaction, in conjunction with or in place of metallic aluminium, or alternatively it may be extracted with a solvent such as a petroleum fraction, amyl alcohol or phenol, whereby coloured fluorescent substances are extracted.  The chlorinated hydrocarbon material may be a chlorinated kerosene fraction, chlorinated paraffin wax, chlorinated petrolatum, or other chlorinated liquid or solid hydrocarbon containing at least ten carbon atoms and derived from coal, coal tars, shale oils or petroleum.  The aromatic hydrocarbon may be benzene or a homologue, naphthalene or other polycyclic aromatic hydrocarbon, or material containing aromatic hydrocarbons such as aromatic oils derived from coal or petroleum, aromatic extracts obtained by solvent processes of refining hydrocarbon oils, such as Edeleanu sulphur-dioxide extract, or aromatic liquids obtained by the pyrolysis of liquid or gaseous hydrocarbons.  In the examples: (1) paraffin wax is chlorinated at 80--100 DEG  C. in the presence of iodine until the product contains 10 per cent of chlorine; the chlorinated wax is heated to 100--120 DEG  C. with toluene and aluminium filings in the presence of a petroleum fraction of b.p. 100--120 DEG  C., and the liquid product is isolated as described above; (2) chlorinated paraffin wax containing 17,5 per cent of chlorine is heated to 100--120 DEG  C. with benzene and the sludge obtained from the process of example 1 in the presence of the same hydrocarbon diluent, and the liquid product is isolated as described above; (3) chlorinated paraffin wax containing 25 per cent of chlorine is condensed with benzene, as in example 1; (4) as in example 3, except that toluene is used in place of benzene, and the sludge is extracted with a petroleum fraction of b.p. 60--80 DEG  C.; (5) chlorinated paraffin wax containing 25 per cent of chlorine is heated to 150--200 DEG  C. with naphthalene and aluminium turnings in the presence of a kerosene fraction of b.p. 150--300 DEG  C., and the product is isolated as described above. Specifications 397,169, 401,341, 415,065, [Group III], and 415,526 are referred to.  The Provisional Specification refers to the production of viscous liquid products from organic chlorides, including chlorinated petroleum and coal-tar products, by treating such materials with aluminium and treating the product with water or an unsaturated or aromatic hydrocarbon; the original reaction mixture may also include unsaturated or aromatic hydrocarbons, or phenols. Examples are given in which (1) amyl chloride and xylene are heated with aluminium and the product is treated with water; (2) chlorocyclohexane and naphthalene are heated with aluminium and the product is treated with water; (3) a mixture of 1-, 2- and 3-chloropentanes is heated with aluminium and the product is treated with water.ALSO:Viscous liquids useful as lubricating-oils or as additions to other lubricating oils are prepared by treating chlorinated hydrocarbons containing at least ten carbon atoms with aromatic hydrocarbons in the presence of metallic aluminium (as distinct from activated aluminium), and separating the liquid product from the reaction sludge.  The reaction may be effected at atmospheric or raised temperature in the presence or absence of a nonaromatic hydrocarbon diluent.  A small proportion of iodine may be added, to start the reaction.  The separated liquid product may be refined by washing with water and/or dilute acid and/or dilute alkali, followed if desired by treatment with an adsorbent such as a bleaching earth; the diluent, if used, is then removed by distillation and the product is optionally refined further, as by vacuum distillation.  The reaction sludge may be used as a catalyst in the reaction, in conjunction with or in place of metallic aluminium, or alternatively it may be extracted with a solvent such as a petroleum fraction, amyl alcohol or phenol, whereby coloured fluorescent substances are extracted; these substances may be used to impart bloom or fluorescence to the liquids produced as described above or to other lubricating oils. The chlorinated hydrocarbon material may be a chlorinated kerosene fraction, chlorinated paraffin wax, chlorinated petrolatum, or other chlorinated liquid or solid hydrocarbon containing at least ten carbon atoms and derived from coal, coal tars, shale oils or petroleum.  The aromatic hydrocarbon may be benzene or a homologue, naphthalene or other polycyclic aromatic hydrocarbon, or material containing aromatic hydrocarbons such as aromatic oils derived from coal or petroleum, aromatic extracts obtained by solvent processes of refining hydrocarbon oils such as Edeleanu sulphur-dioxide extract, or aromatic liquids obtained by the pyrolysis of liquid or gaseous hydrocarbons.  In the examples: (1) paraffin wax is chlorinated at 80--100 DEG  C., in the presence of iodine until the product contains 10 per cent of chlorine; the chlorinated wax is heated to 100--120 DEG  C. with toluene and aluminium filings in the presence of a petroleum fraction of b.p. 100--120 DEG  C., and the liquid product is isolated as described above; certain physical properties of the product, before and after vacuum distillation, and of a mixture of the distilled product with a lubricating oil of high pourpoint, are stated; (2) chlorinated paraffin wax containing 17,5 per cent of chlorine is heated to 100--120 DEG  C., with benzene and the sludge obtained from the process of example 1 in the presence of the same hydrocarbon diluent, and the liquid product is isolated as described above; certain of its physical properties are stated; (3) chlorinated paraffin wax containing 25 per cent of chlorine is condensed with benzene as in example 1; certain physical properties of the product, and of a mixture thereof with a lubricating oil, are stated; (4) as in example 3, except that toluene is used in place of benzene; certain physical properties of the product are stated; the sludge is extracted with a petroleum fraction of b.p. 60--80 DEG  C., and the extract is added to the viscous liquid product; (5) chlorinated paraffin wax containing 25 per cent of chlorine is heated to 150--200 DEG  C., with naphthalene and aluminium turnings in the presence of a kerosene fraction of b.p. 150--300 DEG  C., and the product is isolated as described above; certain of its physical properties are stated.  Specifications 397,169, 401,341, 415,065, and 415,526 are referred to.  The Provisional Specification refers to the production of viscous liquid products from organic chlorides, including chlorinated petroleum and coal-tar products, by treating such materials with aluminium and treating the product with water or an unsaturated or aromatic hydrocarbon; the original reaction mixture may also include unsaturated or aromatic hydrocarbons, or phenols. Examples are given in which (1) amyl chloride and xylene are heated with aluminium and the product is treated with water; (2) chlorocyclohexane and naphthalene are heated with aluminium and the product is treated with water; (3) a mixture of 1-, 2- and 3-chloropentanes is heated with aluminium and the product is treated with water.