Patent GB-777497-A (GB)
Title: Process for the production of terephthalic acid, its nuclear substitution products and salts thereof
IPC: B21B1/16
Filed: 1954-12-31
Abstract: Terephthalic acid or its nuclear substitution products are prepared by heating an alkali-metal salt of a benzene dicarboxylic acid in which the carboxyl groups are not in the paraposition to one another, or a mixture of such salts, or a mixture of phthalic anhydride and an alkali-metal carbonate, to a temperature between 350 DEG  and 550 DEG C. in the presence of a catalyst containing cadmium or zinc to obtain an alkali-metal salt of terephthalic acid or a nuclear substitution product thereof, and liberating the free acid therefrom.  Benzene dicarboxylic acids mentioned are phthalic acid and isophthalic acid and their nuclear substitution products. Catalysts specified are metallic cadmium and zinc, cadmium/magnesium alloy, the oxides, iodides, chlorides, fluorides, sulphates, phosphates, carbonates, acetates, benzoates, phthalates, isophthalates, and terephthalates of cadmium and zinc, cadmium sulphide, zinc silicofluoride, zinc nitrate, zinc cyanide, and cadmium or zinc soaps or mixtures thereof. Catalyst carriers may be used.  The reaction may be carried out by heating the materials in dry powder form under ordinary, increased or reduced pressures in the presence of inert gases such as carbon dioxide, nitrogen or methane.  Inert solids such as sand, carbon, e.g. coke, potassium carbonate, potassium sulphate, potassium chloride, or metal powders, turnings, or fragments which do not catalyse the reaction may be present.  The reaction chamber may be divided into compartments by horizontal and/or vertical partitions of metal, or the reaction mixture may be stirred or ground in a rolling furnace during the reaction or heated in kneading machines.  The process may be continuous.  The products may be isolated by dissolving the reaction mixture in water and treating the solution with mineral acid.  The crude product filtered off may then be repeatedly extracted with boiling water leaving terephthalic acid as an insoluble residue.  Alternative separation is by sublimation of the acids or by distillation of their methyl esters.  Terephthalic acid and monopotassium phthalate may be recovered from a crude reaction product containing di-potassium terephthalate by heating it with phthalic anhydride and water: <FORM:0777497/IV(b)/1> After removal of the solid terephthalic acid, the solution of mono-potassium phthalate is neutralized with potassium hydroxide, the water evaporated and the di-potassium phthalate used as starting material in a subsequent conversion.  In examples (1-21, 23-33, 38-49), the following are heated with a catalyst or mixture of catalysts selected from those mentioned above, under a carbon dioxide atmosphere at normal or increased pressures: di-potassium phthalate, dipotassium isophthalate, di-sodium phthalate, a mixture of di-potassium phthalate and isophthalate, a mixture of di-potassium isophthalate and terephthalate, a mixture of the di-potassium salts of phthalic, isophthalic and terephthalic acids, and mixtures of phthalic anhydride with sodium, potassium or lithium carbonates; (22), di-potassium phthalate and cadmium oxide are heated in vacuo; (34), phthalic anhydride vapour is passed over heated potassium carbonate mixed with cadmium fluoride; (35), di-potassium phthalate and cadmium fluoride are heated as a precompressed mass in an open vessel; (36), di-potassium phthalate and cadmium oxide are heated in the absence of an atmosphere under mechanical pressure supplied by a piston; and (37), the recovery of terephthalic acid by heating a reaction product with phthalic anhydride and water is illustrated; in all examples terephthalic acid being isolated from the reaction mixtures, and in examples (5), (14) and (32) trimesic and benzoic acids also being obtained.  Specifications 747,204, 762,448 and 762,644 are referred to.