Processes for producing aromatic dicarboxylic acids
View Patent ↗Processes for producing aromatic dicarboxylic acids are disclosed, the processes including a step of combining in a reaction medium a dialkyl aromatic, a solvent comprising water and a saturated organic acid having from 2-4 carbon atoms, and an oxygen-containing gas, at a temperature from about 125° C. to about 155° C., in the presence of a catalyst composition comprising cobalt, manganese, zirconium, and bromine, wherein the weight ratio of cobalt to manganese in the reaction mixture is from about 10 to about 400. The processes provide improved conversion, while reducing the formation of carbon oxides and other by-products.
1. A process for producing an aromatic dicarboxylic acid, the process comprising combining in a reaction medium a dialkyl aromatic, a solvent comprising water and a saturated organic acid having from 2-4 carbon atoms, and an oxygen-containing gas, at a temperature from 130° C. to 150° C., in the presence of a catalyst composition comprising cobalt, manganese, zirconium, and bromine, wherein the weight ratio of cobalt to manganese in the reaction mixture is from about 10 to about 400, wherein zirconium is present in an amount ranging from 300 ppm to 1500 ppm with respect to the weight of the liquid in the reaction medium.
2. The process according to claim 1 , wherein the weight ratio of cobalt to manganese in the reaction mixture is from about 12 to about 300.
3. The process according to claim 1 , wherein the weight ratio of cobalt to manganese in the reaction mixture is from about 15 to about 250.
4. The process according to claim 1 , wherein the dialkyl aromatic comprises p-xylene and the aromatic dicarboxylic acid produced comprises terephthalic acid.
5. The process according to claim 1 , wherein the saturated organic acid comprises acetic acid.
6. The process according to claim 1 , wherein the zirconium is provided as one or more of: zirconium oxide, zirconium bromide, zirconium chloride, zirconium acetate, zirconium acetate hydroxide, zirconium acetylacetonate, zirconium hydroxide, zirconium butoxide, zirconium propoxide, or zirconyl acetate.
7. The process according to claim 1 , wherein the zirconium is provided as zirconium acetate, zirconium acetate hydroxide, or zirconyl acetate.
8. The process according to claim 1 , wherein the oxygen-containing gas comprises air.
9. The process according to claim 1 , wherein the cobalt is provided in an amount from about 500 ppm to about 6,000 ppm, with respect to the weight of liquid in the reaction medium.
10. The process according to claim 1 , wherein the cobalt is provided in an amount from about 750 ppm to about 4,500 ppm, with respect to the weight of liquid in the reaction medium.
11. The process according to claim 1 , wherein the cobalt is provided in an amount from about 1,000 ppm to about 4,000 ppm, with respect to the weight of liquid in the reaction medium.
12. The process according to claim 1 , wherein the manganese is provided in an amount from about 20 ppm to about 425 ppm, with respect to the weight of liquid in the reaction medium.
13. The process according to claim 1 , wherein the manganese is provided in an amount from about 20 ppm to about 300 ppm, with respect to the weight of liquid in the reaction medium.
14. The process according to claim 1 , wherein the manganese is provided in an amount from about 20 ppm to about 200 ppm, with respect to the weight of liquid in the reaction medium.
15. The process according to claim 1 , wherein the bromine is provided in an amount from about 750 ppm to about 6,000 ppm, with respect to the weight of liquid in the reaction medium.
16. The process according to claim 1 , wherein the bromine is provided in an amount from about 900 ppm to about 5,000 ppm, with respect to the weight of liquid in the reaction medium.
17. The process according to claim 1 , wherein the bromine is provided in an amount from about 1,000 ppm to about 4,500 ppm, with respect to the weight of liquid in the reaction medium.
18. The process according to claim 1 , wherein the weight ratio of cobalt to bromine is from about 0.6 to about 10.
19. The process according to claim 1 , wherein the weight ratio of cobalt to bromine is from about 0.7 to about 8.
20. The process according to claim 1 , wherein the weight ratio of cobalt to bromine is from about 0.8 to about 5.
21. The process according to claim 1 , wherein the process produces no more than about 1.2 moles CO X per mole of dialkyl aromatic provided to the reaction medium.
22. The process according to claim 1 , wherein zirconium is present in an amount of at least 460 ppm with respect to the weight of the liquid in the reaction medium.
23. The process according to claim 1 , wherein zirconium is present in an amount of at least 610 ppm with respect to the weight of the liquid in the reaction medium.
24. The process according to claim 1 , wherein zirconium is present in an amount in the range of from about 460 to about 1,250 ppm with respect to the weight of the liquid in the reaction medium.
25. The process according to claim 1 , wherein zirconium is present in an amount in the range of from about 610 to about 1,000 ppm with respect to the weight of the liquid in the reaction medium.