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 one or more compounds of formula I:
wherein each R 1 and R 2 is independently hydrogen or alkyl, the method comprising:
combining one or more compounds of formula A:
one or more compounds of formula B:
any combination of one or more compounds of formula A and one or more compounds of formula B, wherein R 1 and R 2 in formulae A and B are as defined in formula I above, with
(i) ethylene, and
(ii) a sulfonic acid, or an ester, anhydride or resin thereof, or
a sulfonimide or a sulfonimide salt,
to produce one or more compounds of formula I from at least a portion of the one or more compounds of formula A, the one or more compounds of formula B, or any combinations thereof, and at least a portion of the ethylene.
2. The method of claim 1 , wherein each R 1 and R 2 is independently alkyl; or R 1 is alkyl and R 2 is hydrogen.
3. The method of claim 1 , wherein:
the sulfonic acid has a structure of formula R x SO 3 H;
wherein R x is alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl,
wherein each alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl is optionally substituted with 1 to 8 substituents independently selected from the group consisting of alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, nitro, —OR′, —C(O)OR′, —C(O)NR′R″, —CHO, —COR′, and cyano,
wherein each R′ and R″ is independently hydrogen, alkyl, or haloalkyl.
4. The method of claim 1 , wherein:
the sulfonimide has a structure of formula (R y1 SO 2 )NH(SO 2 R y2 ); and
the sulfonimide salt has a structure of formula Q r+ [(R y1 SO 2 )N(R y2 SO 2 )] r ,
wherein each R y1 and R y2 is independently alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl,
wherein each alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl is optionally substituted with 1 to 8 substituents independently selected from the group consisting of alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, nitro, —OR′, —C(O)OR′, —C(O)NR′R″, —CHO, —COR′, and cyano,
wherein each R′ and R″ is independently hydrogen, alkyl, or haloalkyl,
Q (if present) is a cation; and
r (if present) is the charge of the cation.
5. The method of claim 4 , wherein Q r+ is Al 3+ , Bi 3+ , Cu 2+ , Cu + , Cr 3+ , Fe 3+ , Gd 3+ , In 3+ , Ni 2+ , Nd 3+ , Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ba 2+ , Ca 2+ , La 3+ , Sc 3+ , Ti 4+ , V 5+ , Y 3+ , Zn 2+ , Pt 2+ , Pd 2+ , Ag + , Au 3+ , Tl 3+ , Tl + , Re 3+ , Hg 2 2+ , Hg 2+ , NH 4 + , Sn 4+ , Sn 3+ , Sn 2+ , B 3+ , Ga 3+ , Pb 4+ , Pb 2+ , CO 3+ , CO 2+ , Ge 4+ , Ge 2+ , Ce 4+ , or Ce 3+ .
6. The method of claim 1 , wherein the sulfonic acid or resin thereof, or the sulfonimide or the sulfonimide salt is CF 3 SO 3 H, HCF 2 CF 2 SO 3 H, C 6 F 5 SO 3 H, 4-methylbenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, NH(Tf) 2 , Al[N(Tf) 2 ] 3 , Bi[N(Tf) 2 ] 3 , Cu[N(Tf) 2 ] 2 , Cu[N(Tf) 2 ], Cr[N(Tf) 2 ] 3 , Fe[N(Tf) 2 ] 3 , Gd[N(Tf) 2 ] 3 , In[N(Tf) 2 ] 3 , Ni[N(Tf) 2 ] 2 , Nd[N(Tf) 2 ] 3 , Li[N(Tf) 2 ], Na[N(Tf) 2 ], K[N(Tf) 2 ], Rb[N(Tf) 2 ], Cs[N(Tf) 2 ], Mg[N(Tf) 2 ] 2 , Ba[N(Tf) 2 ] 2 , Ca[N(Tf) 2 ] 2 , La[N(Tf) 2 ] 3 , Sc[N(Tf) 2 ] 3 , Ti[N(Tf) 2 ] 4 , V[N(Tf) 2 ] 5 , Y[N(Tf) 2 ] 3 , Zn[N(Tf) 2 ] 2 , Pt[N(Tf) 2 ] 2 , Pd[N(Tf) 2 ] 2 , Ag[N(Tf) 2 ], Ag[N(Tf) 2 ] 2 , Au[N(Tf) 2 ] 3 , Tl[N(Tf) 2 ] 3 , Tl[N(Tf) 2 ], Re[N(Tf) 2 ] 3 , Hg 2 [N(Tf) 2 ] 2 , Hg[N(Tf) 2 ] 2 , NH 4 [N(Tf) 2 ], Sn[N(Tf) 2 ] 4 , Sn[N(Tf) 2 ] 3 , Sn[N(Tf) 2 ] 2 , B[N(Tf) 2 ] 3 , Ga[N(Tf) 2 ] 3 , Pb[N(Tf) 2 ] 4 , Pb[N(Tf) 2 ] 2 , Co[N(Tf) 2 ] 3 , Co[N(Tf) 2 ] 2 , Ge[N(Tf) 2 ] 4 , Ge[N(Tf) 2 ] 3 , Ge[N(Tf) 2 ] 2 , Ge[N(Tf) 2 ], Ce[N(Tf) 2 ] 4 , Ce[N(Tf) 2 ] 3 , ethyldimethylpropylammonium bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, triethylsulfonium bis(trifluoromethylsulfonyl)imide, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide, [(C 6 H 13 ) 3 (C 14 H 29 )P] + [(CF 3 SO 2 ) 2 N] − , [C 11 H 16 N] + [N(SO 2 CF 3 ) 2 ] − , [C 8 H 15 N 2 ] + [N(SO 2 CF 3 ) 2 ] − , [C 6 H 11 N 2 ] + [N(SO 2 CF 2 CF 3 ) 2 ] − , [C 6 H 11 N 2 ] + [N(SO 2 CF 3 ) 2 ] − , or [C 6 H 14 N] + [N(SO 2 CF 3 ) 2 ] − , or any combinations thereof.
7. The method of claim 1 , wherein R 1 and R 2 are each alkyl.
8. The method of claim 7 , wherein R 1 and R 2 are each methyl.
9. The method of claim 1 , further comprising combining a solvent system with the compound of formula A, the compound of formula B, or any combination thereof, the ethylene, and the sulfonic acid, or an ester, anhydride or resin thereof, or the sulfonimide or the sulfonimide salt.
10. The method of claim 9 , wherein the solvent system comprises an alkyl phenyl solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, an ionic liquid, or any combinations or mixtures thereof.
11. The method of claim 9 , wherein the solvent system comprises dimethylacetamide, acetonitrile, sulfolane, dioxane, dimethyl ether, diethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, polyglyme, proglyme, higlyme, tetrahydrofuran, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, triacetin, dibutylphthalate, butane, pentane, cyclopentane, hexane, cyclohexane, heptane, cycloheptane, octane, cyclooctane, nonane, decane, undecane, dodecane, hexadecane, tetrachloride, chloroform, dichloromethane, nitromethane, toluene, anisole, nitrobenzene, bromobenzene, methylpyrrole, methylpyrrolidone, dimethylfuran, dichlorobenzene, para-xylene, mesitylene, dodecylbenzene, pentylbenzene, hexylbenzene, diphenyl ether, methyldiphenyl ether, ethyldiphenyl ether, water, or any combinations or mixtures thereof.
12. The method of claim 1 , wherein:
R 1 and R 2 are each methyl; and
the one or more compounds of formula A, one or more compounds of formula B, or any combinations thereof, and the ethylene are combined with a sulfonic acid or a resin thereof.
13. The method of claim 12 , wherein:
the sulfonic acid is triflic acid.
14. The method of claim 13 , wherein the solvent system comprises para-xylene.
15. The method claim 1 , wherein the sulfonimide salt comprises a metal.
16. The method of claim 1 , wherein the sulfonic acid or resin thereof, or the sulfonimide or the sulfonimide salt is produced in situ.
17. The method of claim 9 , wherein the solvent system comprises aliphatic solvent.
18. The method of claim 9 , wherein the solvent system comprises aromatic solvent.
19. The method of claim 9 , wherein the solvent system comprises alkyl phenyl solvent.
20. The method of claim 13 , wherein the solvent system comprises C4-C30 alkyl solvent.
21. The method of claim 1 , wherein the one or more compounds of formula A, the one or more compounds of formula B, or any combinations thereof, and the ethylene are combined with a sulfonic acid.
22. The method of claim 1 , wherein the one or more compounds of formula A, the one or more compounds of formula B, or any combinations thereof, and the ethylene are combined with a sulfonic acid resin.
23. The method of claim 1 , wherein the one or more compounds of formula A, the one or more compounds of formula B, or any combinations thereof, and the ethylene are combined with a sulfonimide or a sulfonimide salt.
24. The method of claim 3 , wherein:
R x is alkyl, haloalkyl, cycloalkyl, or aryl,
wherein each alkyl, haloalkyl, cycloalkyl, or aryl is optionally substituted with 1 to 8 substituents independently selected from the group consisting of alkyl, haloalkyl, cycloalkyl and aryl.
25. The method of claim 4 , wherein:
each R y1 and R y2 is independently alkyl, haloalkyl, cycloalkyl, or aryl,
wherein each alkyl, haloalkyl, cycloalkyl, or aryl is optionally substituted with 1 to 8 substituents independently selected from the group consisting of alkyl, haloalkyl, cycloalkyl and aryl.
26. A method for producing one or more compounds of formula I:
wherein each R 1 and R 2 is independently hydrogen or alkyl, the method comprising combining:
one or more compounds of formula A:
or one or more compounds of formula B:
or any combination of one or more compounds of formula A and one or more compounds of formula B, wherein R 1 and R 2 in formulae A and B are as defined in formula I above,
with
(i) ethylene, and
(ii) R x1 CF 2 SO 3 H, wherein R x1 is alkyl or haloalkyl,
to produce one or more compounds of formula I from at least a portion of the one or more compounds of formula A, the one or more compounds of formula B, or any combinations thereof, and at least a portion of the ethylene.
27. A method for producing one or more compounds of formula I:
wherein each R 1 and R 2 is independently hydrogen or alkyl, the method comprising combining:
one or more compounds of formula A:
or one or more compounds of formula B:
or any combination of one or more compounds of formula A and one or more compounds of formula B, wherein R 1 and R 2 in formulae A and B are as defined in formula I above,
with:
(i) ethylene, and
(ii) a sulfonamide or a sulfonamide salt, wherein:
the sulfonamide has a structure of formula (R y1 SO 2 )NH 2 or (R y1 SO 2 )NH(R z ); and
the sulfonamide salt has a structure of formula Q r+ [(R y1 SO 2 )N(R z )] r or Q r+ [(R y1 SO 2 )NH] r ;
wherein each R y1 , R y2 and R z is independently alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl,
wherein each alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl is optionally substituted with 1 to 8 substituents independently selected from the group consisting of alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, nitro, —OR′, —C(O)OR′, —C(O)NR′R″—CHO, —COR′, and cyano,
wherein each R′ and R″ is independently hydrogen, alkyl, or haloalkyl,
Q (if present) is a cation; and
r (if present) is the charge of the cation,
to produce one or more compounds of formula I from at least a portion of the one or more compounds of formula A, the one or more compounds of formula B, or any combinations thereof, and at least a portion of the ethylene.
28. The method of claim 27 , wherein:
each R y1 , R y2 and R z is independently alkyl, haloalkyl, cycloalkyl, or aryl,
wherein each alkyl, haloalkyl, cycloalkyl, or aryl is optionally substituted with 1 to 8 substituents independently selected from the group consisting of alkyl, haloalkyl, cycloalkyl and aryl.