公开(公告)号：US4410449A

公开(公告)日：1983-10-18

申请号：US407619

申请日：1982-08-12

Applicant: Karl-Heinz Diessel ,  Rudolf Modic ,  Friedrich Struss

Inventor： Karl-Heinz Diessel ,  Rudolf Modic ,  Friedrich Struss

IPC: C01G45/00 ,  B01J23/92 ,  B01J23/94 ,  B01J31/40 ,  B01J38/00 ,  C01G51/00 ,  C07C67/39 ,  B01J1/04 ,  C07C51/42 ,  C07C69/82

CPC classification number: B01J31/04 ,  B01J23/92 ,  B01J31/4015 ,  B01J31/403 ,  C07C67/39 ,  B01J2231/70 ,  B01J23/00 ,  B01J2531/72 ,  B01J2531/845 ,  Y02P20/584

Abstract: A process for the recovery and reuse of a heavy-metal oxidation catalyst solution from a high-boiling distillation residue having a cobalt content of 1-10 g/kg of residue is disclosed. The distillation residue is obtained in the production of dimethyl terephthalate by the oxidation of mixtures containing p-xylene and/or methyl p-toluate in the liquid phase with oxygen or an oxygen-containing gas under an elevated pressure and at an elevated temperature in the presence of dissolved heavy-metal oxidation catalyst, by subsequent esterification of the oxidation product with methanol and by a distillatory separation of the esterification product into a fraction rich in methyl p-toluate, a fraction rich in dimethyl terephthalate, and the high-boiling distillation residue. The process involves the steps of effecting extraction of the heavy-metal oxidation catalyst from the high-boiling distillation residue with aqueous low-molecular aliphatic monocarboxylic acids under heating; treating the aqueous, acidic extract, which contains the heavy-metal oxidation catalyst and has a cobalt content with a strongly acidic cation exchange resin in the alkali metal form at an elevated temperature until the exchange capacity has been reached, and washing the cation exchange resin at an elevated temperature with water and regenerating the cation exchange resin at room temperature with a solution containing Na.sup.+ or K.sup.+ acetate to displace the catalyst components and to obtain an aqueous acetic acid catalyst solution containing the catalyst components.

Abstract translation: 公开了一种重金属氧化催化剂溶液从钴含量为1-10克/公斤残留物的高沸点蒸馏残渣中回收和再利用的方法。 通过在液相中在氧气或含氧气体中在升高的压力下和在高温下氧化含有对二甲苯和/或对甲苯甲酸甲酯的混合物在生产对苯二甲酸二甲酯中获得蒸馏残余物。 存在溶解的重金属氧化催化剂，随后用甲醇对氧化产物进行酯化，并将酯化产物蒸馏分离成富甲苯甲酸甲酯，富含对苯二甲酸二甲酯的馏分和高沸点蒸馏 残留物 该方法包括在加热下用低分子量脂族单羧酸水溶液从高沸点残渣中萃取重金属氧化催化剂的步骤; 处理含有重金属氧化催化剂的水性酸性提取物，并在高温下与碱金属形式的强酸性阳离子交换树脂具有钴含量，直到达到交换容量，并洗涤阳离子交换树脂 在高温下用水，并在室温下用含有Na +或K +乙酸的溶液再生阳离子交换树脂以置换催化剂组分并获得含有催化剂组分的含水乙酸催化剂溶液。