PROCESS FOR THE DISPROPORTIONATION OF ALKALI METAL AROMATIC CARBOXYLATES

摘要

1436671 Disproportionation of alkali metal aromatic carboxylates PHILLIPS PETROLEUM CO 4 Jan 1974 [5 Jan 1973] 00386/74 Heading C2C [Also in Division C5] Aromatic polycarboxylic acids are obtained by disproportionation and metathesis of an alkali metal salt of aromatic carboxylic acids having at least one less COOH group per molecule than the desired product comprising: (A) dispersing the said alkali metal salt of an aromatic carboxylic acid and a disproportionation catalyst, being a heavy metal salt of an aromatic carboxylic acid in an inert high boiling organic dispersant which is liquid, or which melts under the temperature applied in step B, thereby to form a slurry of said salts in said dispersant, which slurry contains from 25-80% by wt. of dispersant based on the total weight of the slurry; (B) heating the slurry of step (A) under anhydrous conditions and in the absence of free O 2 to effect the disproportionation of said alkali metal sa (c) quenching the reaction mass of step (B) with water thereby to form an organic dispersant phase and an aqueous phase -containing the spent catalyst in suspension and the aromatic polycarboxylic acid salt disproportionation product in solution; (D) separating the aqueous and organic dispersant phases of step (C) and separating from the aqueous phase the spent catalyst; (E) subjecting the separated aqueous phase of step (D) to a metathesis reaction with an aromatic carboxylic acid; (F) recovering from the reaction mass of step (E) the desired aromatic polycarboxylic acid in free acid or salt form; (G) concentrating the aqueous mother liquor from step (F); (H) mixing the concentrated mother liquor from step (G) with additional organic dispersant and evaporating the water from the mixture to form a substantially anhydrous slurry of alkali metal aromatic carboxylic acid salt in said inert organic dispersant; (I) recycling the slurry of step (H) to step (B); (b) mixing the spent catalyst separated in step (D) with additional organic dispersant to form a slurry therein, said slurry containing from 10 to 99À9% by wt. of dispersant, based on the total weight of the slurry; (K) regenerating the catalyst by reacting said slurry of step (J) with additional aromatic carboxylic acid, the regeneration being effected at a mole ratio of aromatic carboxylic acid to spent catalyst in the range 1À9 : 1 to 2À1 : 1 and at a temperature in the range 125-260‹ C.; and (L) recycling the regenerated catalyst of step (K) to step (B). The process is illustrated by the conversion of benzoic acid to terephthalic acid. Specified classes of dispersants are polyaromatio hydrocarbons having three or more separate aromatic rings or polynuclear aromatic hydrocarbons having two or more fused aromatic rings. Specified aromatic carboxylic acids used as starting materials are benzoic acid, 2-naphthoic acid, 4-biphenyl carboxylic acid, 2,6-naphthalene dicarboxylic acid, phthalic acid, isophthalic acid, krephthalic acid, 2-anthracene carboxylic acid, 1,5-anthracenedicarboxylic acid, 1,5,9- anthracenetricarboxylic acid, 3-phenanthrenecarboxylic acid, 2,3,4-trimethylbenzenecarboxylic acid, 2,4,6-trimethylbenzene-1,3-dicarboxylic acid, 2-ethyl-4-hexyl-6-methylbenzene- 1,3-dicarboxylic acid and 2,4-dibutylbenzene- 1,3,5-tricarboxylic acid. The heavy metal salts used as disproportionation catalysts may be salts of Zn, Cd, Hg, Pb, Fe, Mn, Mg, Ca or Cr.