Process for production of hexanetriol from 5-hydroxymethylfurfural
Industrial scale conversions of 5-hydroxymethylfurfural to commodity chemicals such as 1,2,6-hexanetriol and 1,6-hexanediol by chemocatalytic conversions using hydrogen and a heterogeneous reduction catalyst are provided. The reactions are suitable for use in continuous flow reactors. Methods of carrying out the conversions are provided, as are product and catalyst compositions.
1. A process for preparing 2,5-bis-hydroxymethylfuran (BHMF) from 5-hydroxymethylfurfural (HMF) comprising:
reacting the 5-hydroxymethylfurfural (HMF) with hydrogen in a continuous flow reactor in the presence of an organic solvent and a heterogeneous reduction catalyst comprising Cu to form the 2,5-bis-hydroxymethylfuran (BHMF) over an on-stream period of at least 150 hours.
2. A process for preparing 2,5-bis-hydroxymethylfuran (BHMF) from 5-hydroxymethylfurfural (HMF) comprising:
reacting the 5-hydroxymethylfurfural (HMF) with hydrogen in a continuous flow reactor in the presence of an organic solvent and a heterogeneous reduction catalyst comprising Pt to form the 2,5-bis-hydroxymethylfuran (BHMF) over an on-stream period of at least 150 hours.
3. The process of claim 1 , wherein the heterogeneous reduction catalyst further comprises a modifier.
4. The process of claim 3 , wherein the modifier is selected from the group consisting of Mn, Co, Au, W, Cu, Zn, Mo, Sb, Bi and Pb.
5. The process of claim 1 , wherein the heterogeneous reduction catalyst comprises a combination of metals selected from the group consisting of Co—Cu and Ni—Cu.
6. The process of claim 1 , wherein the heterogeneous reduction catalyst further comprises a catalyst support.
7. The process of claim 6 , wherein the catalyst support is selected from the group consisting of carbons, aluminas, zirconias, silicas, alumina-silicas, titanias, alumina-titanias, silicon carbides and mixed phases thereof.
8. The process of claim 1 , wherein the heterogeneous reduction catalyst further comprises an alumina catalyst support.
9. The process of claim 1 further comprising:
feeding the 5-hydroxymethylfurfural (HMF) through a guard bed comprising a transition metal to the continuous flow reactor.
10. The process of claim 9 , wherein the guard bed comprises at least one transition metal selected from the group consisting of Ag, Zn, Cu, Fe, Ni, Co and Pb or a salt or combination thereof.
11. The process of claim 9 , wherein the guard bed comprises at least one transition metal selected from the group consisting of Ag, Zn, Cu and Pb or a salt or combination thereof.
12. The process of claim 1 , wherein the process comprises feeding the 5-hydroxymethylfurfural (HMF) to the continuous flow reactor at a concentration of greater than about 6 weight percent in the organic solvent.
13. The process of claim 1 , wherein the 2,5-bis-hydroxymethylfuran (BHMF) is formed with at least about 90% selectivity and at least 85% conversion of the 5-hydroxymethylfurfural (HMF).
14. The process of claim 1 , wherein the process comprises forming the 2,5-bis-hydroxymethylfuran (BHMF) with at least about 90% selectivity and at least 90% 5-hydroxymethylfurfural (HMF) conversion.
15. The process of claim 1 , wherein the process comprises forming the 2,5-bis-hydroxymethylfuran (BHMF) with at least about 95% selectivity and at least 90% 5-hydroxymethylfurfural (HMF) conversion.
16. The process of claim 1 , wherein the organic solvent comprises less than about 25 weight % water.
17. The process of claim 1 , wherein the organic solvent comprises from about 5 weight % to about 20 weight % water.
18. The process of claim 1 , wherein the 5-hydroxymethylfurfural (HMF) is reacted with hydrogen at a temperature in a range of about 50° C. to about 150° C. and at a pressure in a range of about 50 psi to about 2000 psi.
19. The process of claim 1 , wherein:
the 5-hydroxymethylfurfural (HMF) is reacted with hydrogen in the continuous flow reactor at a pressure in a range of about 50 psi to about 2000 psi;
the organic solvent comprises less than about 25 weight % water; and
the 2,5-bis-hydroxymethylfuran (BHMF) is formed with at least about 90% selectivity and at least 85% 5-hydroxymethylfurfural (HMF) conversion.
20. The process of claim 1 , further comprising reacting the 2,5-bis-hydroxymethylfuran (BHMF) with hydrogen in a continuous flow reactor in the presence of a heterogeneous reduction catalyst comprising at least one metal selected from the group consisting of Ni, Co, Cu, Ag, Pd, Pt and Ru or a combination thereof to form 2,5-bis-hydroxymethyltetrahydrofuran (BHMTHF).
21. The process of claim 20 , further comprising reacting the 2,5-bis-hydroxymethyltetrahydrofuran (BHMTHF) with hydrogen in a continuous flow reactor in the presence of a heterogeneous reduction catalyst comprising at least one metal selected from the group consisting of Ni, Co, Cu, Ag, Pt and Ru or a combination thereof to form 1,2,6-hexanetriol (HTO).
22. The process of claim 21 , further comprising reacting the 1,2,6-hexanetriol (HTO) with hydrogen in a continuous flow reactor in the presence of a heterogeneous reduction catalyst comprising at least one metal selected from the group consisting of Ni, Co, Cu, Ag, Pt and Ru or a combination thereof to form 1,6-hexanediol (HDO).
23. The process of claim 1 , further comprising reacting the 2,5-bis-hydroxymethylfuran (BHMF) with hydrogen in a continuous flow reactor in the presence of a heterogeneous reduction catalyst comprising at least one metal selected from the group consisting of Ni, Co, Cu, Ag, Pt, Pd and Ru or a combination thereof to form 1,2,6-hexanetriol (HTO).
24. The process of claim 23 , further comprising reacting the 1,2,6-hexanetriol (HTO) with hydrogen in a continuous flow reactor in the presence of a heterogeneous reduction catalyst comprising at least one metal selected from the group consisting of Ni, Co, Cu, Ag, Pt and Ru or a combination thereof to form 1,6-hexanediol (HDO).
25. The process of claim 2 , wherein the heterogeneous reduction catalyst further comprises a modifier.
26. The process of claim 25 , wherein the modifier is selected from the group consisting of Mn, Co, Au, W, Cu, Zn, Mo, Sb, Bi and Pb.
27. The process of claim 2 , wherein the heterogeneous reduction catalyst comprises a combination of metals which is Pt—Au.
28. The process of claim 2 , wherein the heterogeneous reduction catalyst further comprises a catalyst support.
29. The process of claim 28 , wherein the catalyst support is selected from the group consisting of carbons, aluminas, zirconias, silicas, alumina-silicas, titanias, alumina-titanias, silicon carbides and mixed phases thereof.
30. The process of claim 2 , wherein the heterogeneous reduction catalyst further comprises an alumina catalyst support.
31. The process of claim 2 further comprising:
feeding the 5-hydroxymethylfurfural (HMF) through a guard bed comprising a transition metal to the continuous flow reactor.
32. The process of claim 31 , wherein the guard bed comprises at least one transition metal selected from the group consisting of Ag, Zn, Cu, Fe, Ni, Co and Pb or a salt or combination thereof.
33. The process of claim 31 , wherein the guard bed comprises at least one transition metal selected from the group consisting of Ag, Zn, Cu and Pb or a salt or combination thereof.
34. The process of claim 2 , wherein the process comprises feeding the 5-hydroxymethylfurfural (HMF) to the continuous flow reactor at a concentration of greater than about 6 weight percent in the organic solvent.
35. The process of claim 2 , wherein the 2,5-bis-hydroxymethylfuran (BHMF) is formed with at least about 90% selectivity and at least 85% conversion of the 5-hydroxymethylfurfural (HMF).
36. The process of claim 2 , wherein the process comprises forming the 2,5-bis-hydroxymethylfuran (BHMF) with at least about 90% selectivity and at least 90% 5-hydroxymethylfurfural (HMF) conversion.
37. The process of claim 2 , wherein the process comprises forming the 2,5-bis-hydroxymethylfuran (BHMF) with at least about 95% selectivity and at least 90% 5-hydroxymethylfurfural (HMF) conversion.
38. The process of claim 2 , wherein the organic solvent comprises less than about 25 weight % water.
39. The process of claim 2 , wherein the organic solvent comprises from about 5 weight % to about 20 weight % water.
40. The process of claim 2 , wherein the 5-hydroxymethylfurfural (HMF) is reacted with hydrogen at a temperature in a range of about 50° C. to about 150° C. and at a pressure in a range of about 50 psi to about 2000 psi.
41. The process of claim 2 , wherein:
the 5-hydroxymethylfurfural (HMF) is reacted with hydrogen in the continuous flow reactor at a pressure in a range of about 50 psi to about 2000 psi;
the organic solvent comprises less than about 25 weight % water; and
the 2,5-bis-hydroxymethylfuran (BHMF) is formed with at least about 90% selectivity and at least 85% 5-hydroxymethylfurfural (HMF) conversion.
42. The process of claim 2 , further comprising reacting the 2,5-bis-hydroxymethylfuran (BHMF) with hydrogen in a continuous flow reactor in the presence of a heterogeneous reduction catalyst comprising at least one metal selected from the group consisting of Ni, Co, Cu, Ag, Pd, Pt and Ru or a combination thereof to form 2,5-bis-hydroxymethyltetrahydrofuran (BHMTHF).
43. The process of claim 42 , further comprising reacting the 2,5-bis-hydroxymethyltetrahydrofuran (BHMTHF) with hydrogen in a continuous flow reactor in the presence of a heterogeneous reduction catalyst comprising at least one metal selected from the group consisting of Ni, Co, Cu, Ag, Pt and Ru or a combination thereof to form 1,2,6-hexanetriol (HTO).
44. The process of claim 43 , further comprising reacting the 1,2,6-hexanetriol (HTO) with hydrogen in a continuous flow reactor in the presence of a heterogeneous reduction catalyst comprising at least one metal selected from the group consisting of Ni, Co, Cu, Ag, Pt and Ru or a combination thereof to form 1,6-hexanediol (HDO).
45. The process of claim 2 , further comprising reacting the 2,5-bis-hydroxymethylfuran (BHMF) with hydrogen in a continuous flow reactor in the presence of a heterogeneous reduction catalyst comprising at least one metal selected from the group consisting of Ni, Co, Cu, Ag, Pt, Pd and Ru or a combination thereof to form 1,2,6-hexanetriol (HTO).
46. The process of claim 45 , further comprising reacting the 1,2,6-hexanetriol (HTO) with hydrogen in a continuous flow reactor in the presence of a heterogeneous reduction catalyst comprising at least one metal selected from the group consisting of Ni, Co, Cu, Ag, Pt and Ru or a combination thereof to form 1,6-hexanediol (HDO).