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, starch, sugar) and ethylene in the presence of a catalyst. For example, cellulose and/or hemicellulose may be converted into 2,5-dimethylfuran (DMF), which may be converted into para-xylene by cycloaddition of ethylene to DMF. Para-xylene can then be oxidized to form terephthalic acid.
1. A method for producing para-xylene, comprising:
combining 2,5-hexanedione with ethylene and a catalyst to form a reaction mixture, wherein the catalyst comprises a metal cation and a triflate counterion; and
producing para-xylene from at least a portion of the 2,5-hexanedione 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 metal cation is a Group 3 metal cation, a Group 9 metal cation, a Group 10 metal cation, a Group 11 metal cation, or a lanthanide series metal cation.
4. The method of claim 1 , wherein the metal cation is a divalent metal cation or a trivalent metal cation.
5. The method of claim 1 , wherein the metal cation is Cu 2+ , Co 2+ , Cr 3+ , Ni 2+ , Mg 2+ , Zn 2+ , Al 3+ , Bi 3+ , Fe 3+ , Gd 3+ , In 3+ , Nd 3+ , La 3+ , Sc 3+ , or Y 3+ .
6. The method of claim 1 , 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.
7. The method of claim 1 , wherein the 2,5-hexanedione, the ethylene and the catalyst are further combined with a solvent to form the reaction mixture.
8. The method of claim 7 , wherein the solvent comprises an aliphatic solvent, an aromatic solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, a halogenated solvent, an ionic liquid, or any mixtures thereof.
9. The method of claim 7 , wherein the solvent comprises an aliphatic solvent, or an aromatic solvent, or any mixtures thereof.
10. The method of claim 7 , wherein the solvent comprises an aromatic solvent, an ether solvent, or any mixtures thereof.
11. The method of claim 7 , wherein the solvent comprises an aromatic solvent.
12. The method of claim 7 , wherein the solvent comprises dioxane, dimethyl ether, diethyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, butane, pentane, cyclopentane, hexane, cyclohexane, heptane, cycloheptane, octane, cyclooctane, nonane, decane, undecane, dodecane, hexadecane, tetrachloride, chloroform, dichloromethane, nitromethane, para-xylene, toluene, anisole, nitrobenzene, bromobenzene, or N-methylpyrrole, or any combinations thereof.
13. The method of claim 7 , wherein the solvent comprises para-xylene.
14. The method of claim 7 , wherein the solvent comprises 1,4-dioxane and para-xylene.
15. The method of claim 1 , wherein the ethylene is provided at a supercritical pressure, a supercritical temperature, or a combination thereof.
16. The method of claim 1 , wherein the para-xylene is produced at a temperature between 200° C. and 400° C.
17. The method of claim 1 , wherein the para-xylene is produced at a pressure between 50 bar to 1000 bar.
18. The method of claim 1 , wherein the para-xylene is produced at a pressure between 600 psi and 1000 psi.
19. A method for producing terephthalic acid, comprising:
combining 2,5-hexanedione with ethylene and a catalyst to form a reaction mixture, wherein the catalyst comprises a metal cation and a triflate counterion;
producing para-xylene from at least a portion of the 2,5-hexanedione and at least a portion of the ethylene in the reaction mixture; and
oxidizing the para-xylene to produce terephthalic acid.
20. The method of claim 19 , 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.