Methods of producing para-xylene and terephthalic acid
The present disclosure provides methods to produce para-xylene, toluene, and other compounds from renewable sources (e.g., cellulose, hemicellulose) and ethylene in the presence of an acid, such as a Lewis acid. For example, cellulose and/or hemicellulose may be converted into 2,5-dimethylfuran (DMF) and 2-methylfuran, which may be converted into para-xylene and toluene, respectively. In particular, para-xylene can then be oxidized to form terephthalic acid.
1. A method for producing para-xylene, comprising:
a) combining 2,5-dimethylfuran with ethylene and a catalyst to form a reaction mixture, wherein the catalyst is bismuth triflate, copper triflate, cobalt triflate, chromium triflate, iron triflate, cadmium triflate, indium triflate, nickel triflate, manganese triflate, tin triflate, titanium triflate, vanadium triflate, yttrium triflate, zinc triflate, gadolinium triflate, lanthanum triflate, aluminum triflate, cerium triflate, praseodymium triflate, neodymium triflate, samarium triflate, europium triflate, terbium triflate, dysprosium triflate, holmium triflate, erbium triflate, thulium triflate, ytterbium triflate, or lutetium triflate, or any combinations thereof; and
b) producing para-xylene from at least a portion of the 2,5-dimethylfuran and at least a portion of the ethylene in the reaction mixture.
2. The method of claim 1 , further comprising isolating the para-xylene from the reaction mixture.
3. The method of claim 1 , wherein the 2,5-dimethylfuran, the ethylene and the catalyst are further combined with a solvent to form the reaction mixture.
4. The method of claim 3 , wherein the solvent has a dipole moment above 0.1.
5. The method of claim 3 , wherein the solvent comprises an ether.
6. The method of claim 3 , wherein the solvent comprises dioxane, glyme, diglyme, triglyme, tetraglyme, or tetrahydrofuran, or any mixtures thereof.
7. The method of claim 6 , wherein the solvent comprises 1,4-dioxane.
8. The method of claim 1 , wherein less than 10% of the reaction mixture is 2,5-hexanedione.
9. The method of claim 1 , wherein at least a portion of the 2,5-dimethylfuran is converted to para-xylene at a temperature of at least 150° C.
10. The method of claim 9 , wherein at least a portion of the 2,5-dimethylfuran is converted to para-xylene at a temperature of between 150° C. and 300° C.
11. The method of claim 1 , further comprising adding one or more molecular sieves to the reaction mixture.
12. The method of claim 11 , wherein the one or more molecular sieves has a pore size of 3 Å to 100 Å.
13. A method for producing terephthalic acid, comprising:
a) combining 2,5-dimethylfuran with ethylene and a catalyst to form a reaction mixture, wherein the catalyst is bismuth triflate, copper triflate, cobalt triflate, chromium triflate, iron triflate, cadmium triflate, indium triflate, nickel triflate, manganese triflate, tin triflate, titanium triflate, vanadium triflate, yttrium triflate, zinc triflate, gadolinium triflate, lanthanum triflate, aluminum triflate, cerium triflate, praseodymium triflate, neodymium triflate, samarium triflate, europium triflate, terbium triflate, dysprosium triflate, holmium triflate, erbium triflate, thulium triflate, ytterbium triflate, or lutetium triflate, or any combinations thereof;
b) producing para-xylene from at least a portion of the 2,5-dimethylfuran and at least a portion of the ethylene in the reaction mixture; and
c) oxidizing the para-xylene to produce terephthalic acid.
14. A method for producing a compound of formula I, wherein formula I has the structure:
wherein each R 1 and R 2 is independently hydrogen or alkyl, and wherein the method comprises:
a) combining a compound of formula II with ethylene and a catalyst to form a reaction mixture,
wherein the compound of formula II is:
wherein R 1 and R 2 are as defined for formula I above, and
wherein the catalyst is bismuth triflate, copper triflate, cobalt triflate, chromium triflate, iron triflate, cadmium triflate, indium triflate, nickel triflate, manganese triflate, tin triflate, titanium triflate, vanadium triflate, yttrium triflate, zinc triflate, gadolinium triflate, lanthanum triflate, aluminum triflate, cerium triflate, praseodymium triflate, neodymium triflate, samarium triflate, europium triflate, terbium triflate, dysprosium triflate, holmium triflate, erbium triflate, thulium triflate, ytterbium triflate, or lutetium triflate, or any combinations thereof; and
b) producing a compound of formula I from at least a portion of the compound of formula II and at least a portion of the ethylene in the reaction mixture.
15. The method of claim 14 , wherein R 1 and R 2 are each methyl.
16. The method of claim 14 , wherein R 1 is H and R 2 is methyl.
17. The method of claim 14 , wherein the 2,5-dimethylfuran, the ethylene and the catalyst are further combined with a solvent to form the reaction mixture.
18. The method of claim 17 , wherein the solvent comprises an ether.
19. The method of claim 17 , wherein the solvent comprises dioxane, tetrahydrofuran, triglyme, tetraglyme, or sulfolane, or any mixtures thereof.
20. The method of claim 19 , wherein the solvent comprises 1,4-dioxane.
21. The method of claim 14 , wherein at least a portion of the compound of formula II is converted to the compound of formula I at a temperature of at least 150° C.
22. The method of claim 14 , further comprising adding one or more molecular sieves to the reaction mixture.
23. The method of claim 14 , wherein less than 10% of the reaction mixture is a compound of formula III, wherein formula III has the structure
24. The method of claim 3 , wherein the solvent comprises a C 1 to C 10 alcohol, a C 2 to C 6 ketone, a C 2 to C 10 ester, a C 2 to C 10 ether, a chlorinated solvent, a C 1 to C 10 aliphatic solvent, or a C 6 to C 12 aromatic solvent, or any mixtures thereof.
25. The method of claim 3 , wherein the solvent comprises a C 6 to C 12 aromatic solvent.
26. The method of claim 17 , wherein the solvent comprises a C 1 to C 10 alcohol, a C 2 to C 6 ketone, a C 2 to C 10 ester, a C 2 to C 10 ether, a chlorinated solvent, a C 1 to C 10 aliphatic solvent, or a C 6 to C 12 aromatic solvent, or any mixtures thereof.
27. The method of claim 17 , wherein the solvent comprises a C 6 to C 12 aromatic solvent.
28. The method of claim 1 , wherein the catalyst is lanthanum triflate, cerium triflate, praseodymium triflate, neodymium triflate, samarium triflate, europium triflate, terbium triflate, dysprosium triflate, holmium triflate, erbium triflate, thulium triflate, ytterbium triflate, or lutetium triflate, or any combinations thereof.
29. The method of claim 1 , wherein the catalyst is yttrium triflate or lanthanum triflate, or a combination thereof.
30. The method of claim 1 , wherein the catalyst is iron triflate.
31. The method of claim 1 , wherein the catalyst is neodymium triflate, yttrium triflate, or copper triflate, or any combination thereof.
32. The method of claim 1 , wherein the catalyst is bismuth triflate, cobalt triflate, chromium triflate, cadmium triflate, indium triflate, nickel triflate, manganese triflate, tin triflate, titanium triflate, vanadium triflate, zinc triflate, gadolinium triflate, or aluminum triflate, or any combination thereof.
33. The method of claim 1 , wherein the catalyst is copper triflate.
34. The method of claim 13 , wherein the catalyst is lanthanum triflate, cerium triflate, praseodymium triflate, neodymium triflate, samarium triflate, europium triflate, terbium triflate, dysprosium triflate, holmium triflate, erbium triflate, thulium triflate, ytterbium triflate, or lutetium triflate, or any combinations thereof.
35. The method of claim 13 , wherein the catalyst is yttrium triflate or lanthanum triflate, or a combination thereof.
36. The method of claim 13 , wherein the catalyst is iron triflate.
37. The method of claim 13 , wherein the catalyst is neodymium triflate, yttrium triflate, or copper triflate, or any combination thereof.
38. The method of claim 13 , wherein the catalyst is bismuth triflate, cobalt triflate, chromium triflate, cadmium triflate, indium triflate, nickel triflate, manganese triflate, tin triflate, titanium triflate, vanadium triflate, zinc triflate, gadolinium triflate, or aluminum triflate, or any combination thereof.
39. The method of claim 13 , wherein the catalyst is copper triflate.
40. The method of claim 14 , wherein the catalyst is lanthanum triflate, cerium triflate, praseodymium triflate, neodymium triflate, samarium triflate, europium triflate, terbium triflate, dysprosium triflate, holmium triflate, erbium triflate, thulium triflate, ytterbium triflate, or lutetium triflate, or any combinations thereof.
41. The method of claim 14 , wherein the catalyst is yttrium triflate or lanthanum triflate, or a combination thereof.
42. The method of claim 14 , wherein the catalyst is iron triflate.
43. The method of claim 14 , wherein the catalyst is neodymium triflate, yttrium triflate, or copper triflate, or any combination thereof.
44. The method of claim 14 , wherein the catalyst is bismuth triflate, cobalt triflate, chromium triflate, cadmium triflate, indium triflate, nickel triflate, manganese triflate, tin triflate, titanium triflate, vanadium triflate, zinc triflate, gadolinium triflate, or aluminum triflate, or any combination thereof.
45. The method of claim 14 , wherein the catalyst is copper triflate.