Methods for producing 5-(halomethyl) furfural
The present disclosure provides methods to produce 5-(halomethyl)furfural, including 5-(chloromethyl)furfural, by acid-catalyzed conversion of biomass. The methods make use of certain organic solvents with temperature-dependent solubility for 5-(halomethyl)furfural. This allows for temperature-dependent phase separation of the 5-(halomethyl)furfural from the reaction mixture. In certain embodiments, solid 5-(halomethyl)furfural may be obtained. The solid 5-(halomethyl)furfural obtained may be amorphous or crystalline.
1. A method comprising:
a) providing a feedstock, an aqueous acid, and an organic solvent, wherein the feedstock comprises six-carbon sugars;
b) combining the feedstock, the aqueous acid, and the organic solvent to form a reaction mixture;
c) converting at least a portion of the feedstock in the reaction mixture into 5-(halomethyl)furfural at a reaction temperature suitable to produce 5-(halomethyl)furfural,
wherein the reaction mixture comprises an organic phase and an aqueous phase,
wherein the organic phase comprises at least a portion of the organic solvent and at least a portion of the 5-(halomethyl)furfural, and wherein the aqueous phase comprises at least a portion of the aqueous acid;
d) separating at least a portion of the organic phase from the aqueous phase of the reaction mixture at a separation temperature, wherein the organic phase comprises at least a portion of the 5-(halomethyl)furfural and at least a portion of the organic solvent at the separation temperature; and
e) cooling the separated organic phase from step (d) to an isolation temperature to produce a multiphasic organic mixture, wherein the isolation temperature is lower than the separation temperature, and
wherein the multiphasic organic mixture comprises one more product phases and a solvent phase at the isolation temperature, wherein the one or more product phases each comprise at least a portion of the 5-(halomethyl)furfural, and wherein the solvent phase comprises at least a portion of the organic solvent.
2. The method of claim 1 , further comprising isolating one or more of the product phases from the solvent phase to isolate 5-(halomethyl)furfural.
3. The method of claim 1 , wherein:
the reaction temperature is between 30° C. and 300° C.;
the separation temperature is between 30° C. and 300° C., and is the same as or below the reaction temperature; and
the isolation temperature is less than 200° C.
4. A method comprising:
a) providing 5-(halomethyl)furfural and an organic solvent;
b) combining the 5-(halomethyl)furfural and the organic solvent at a temperature to form a mixture; and
c) cooling the mixture to an isolation temperature to isolate the 5-(halomethyl)furfural, wherein the isolation temperature is lower than the temperature in step (b).
5. The method of claim 4 , wherein the organic solvent separates from the 5-(halomethyl)furfural as a solid at the isolation temperature, the method further comprising isolating the 5-(halomethyl)furfural from the solid organic solvent.
6. The method of claim 4 , wherein the temperature in step (b) is between 30° C. and 300° C.
7. A method comprising:
a) providing a feedstock, an aqueous acid, and an organic solvent, wherein the feedstock comprises six-carbon sugars;
b) combining the feedstock, the aqueous acid, and the organic solvent to form a reaction mixture;
c) converting at least a portion of the feedstock in the reaction mixture into 5-(halomethyl)furfural at a reaction temperature suitable to produce 5-(halomethyl)furfural,
wherein the reaction mixture comprises an organic phase and an aqueous phase, wherein the organic phase comprises at least a portion of the organic solvent and at least a portion of the 5-(halomethyl)furfural, and wherein the aqueous phase comprises at least a portion of the aqueous acid;
d) separating at least a portion of the organic phase from the aqueous phase of the reaction mixture at a separation temperature, wherein the organic phase comprises at least a portion of the 5-(halomethyl)furfural and at least a portion of the organic solvent at the separation temperature;
e) cooling the separated organic phase from step (d) to a freezing temperature, wherein the separated organic phase is solid at the freezing temperature; and
f) thawing the solid organic phase in step (e) to an isolation temperature, wherein the solid organic phase forms a multiphasic organic mixture at the isolation temperature,
wherein the multiphasic organic mixture comprises one or more product phases and a solvent phase, wherein the one or more product phases each comprise at least a portion of the solid 5-(halomethyl)furfural, and wherein the solvent phase comprises at least a portion of the organic solvent.
8. The method of claim 7 , further comprising isolating one or more of the product phases from the solvent phase to obtain 5-(halomethyl)furfural.
9. The method of claim 7 , wherein:
the freezing temperature is below 0° C.; and
the isolation temperature is between 0° C. and 200° C., and is above the freezing temperature.
10. The method of claim 1 , wherein the organic solvent comprises one or more alkyl groups and one or more phenyl groups.
11. The method of claim 10 , wherein the organic solvent comprises a linear alkylbenzene.
12. The method of claim 11 , wherein the linear alkylbenzene comprises dodecylbenzene, pentylbenzene, or hexylbenzene, or any combinations or mixtures thereof.
13. The method of claim 11 , wherein the linear alkylbenzene comprises a mixture of branched chain isomers.
14. The method of claim 1 , wherein the organic solvent comprises an alkyl phenyl solvent.
15. The method of claim 1 , wherein the 5-(halomethyl)furfural is 5-(chloromethyl)furfural or 5-(bromomethyl)furfural.
16. The method of claim 2 , wherein the isolated 5-(halomethyl)furfural is amorphous or crystalline.
17. The method of claim 4 , wherein the organic solvent comprises one or more alkyl groups and one or more phenyl groups.
18. The method of claim 17 , wherein the organic solvent comprises a linear alkylbenzene.
19. The method of claim 18 , wherein the linear alkylbenzene comprises dodecylbenzene, pentylbenzene, or hexylbenzene, or any combinations or mixtures thereof.
20. The method of claim 18 , wherein the linear alkylbenzene comprises a mixture of branched chain isomers.
21. The method of claim 4 , wherein the organic solvent comprises an alkyl phenyl solvent.
22. The method of claim 4 , wherein the 5-(halomethyl)furfural is 5-(chloromethyl)furfural or 5-(bromomethyl)furfural.
23. The method of claim 5 , wherein the isolated 5-(halomethyl)furfural is amorphous or crystalline.
24. The method of claim 7 , wherein the organic solvent comprises one or more alkyl groups and one or more phenyl groups.
25. The method of claim 24 , wherein the organic solvent comprises a linear alkylbenzene.
26. The method of claim 25 , wherein the linear alkylbenzene comprises dodecylbenzene, pentylbenzene, or hexylbenzene, or any combinations or mixtures thereof.
27. The method of claim 25 , wherein the linear alkylbenzene comprises a mixture of branched chain isomers.
28. The method of claim 7 , wherein the organic solvent comprises an alkyl phenyl solvent.
29. The method of claim 7 , wherein the 5-(halomethyl)furfural is 5-(chloromethyl)furfural or 5-(bromomethyl)furfural.
30. The method of claim 8 , wherein the isolated 5-(halomethyl)furfural is amorphous or crystalline.