Methods for producing butanol
Methods and compositions for producing 1-butanol are described herein. In some examples, the methods can comprise, contacting a reactant comprising ethanol with a catalyst system, thereby producing a product comprising 1-butanol. The catalyst system can comprise, for example, an iridium catalyst and a nickel, copper, and/or zinc catalyst. The nickel, copper, and zinc catalysts can comprise nickel, copper, and/or zinc and a sterically bulky ligand.
1. A method for producing 1-butanol, comprising: contacting a reactant comprising ethanol with a catalyst system, thereby producing a product comprising 1-butanol, wherein the catalyst system comprises:
an iridium catalyst; and
a nickel catalyst comprising nickel, hydroxide, and a ligand, a copper catalyst comprising copper, hydroxide, and a ligand, or a zinc catalyst comprising zinc, hydroxide, and a ligand.
2. The method of claim 1 , wherein the ligand comprises a tripodal ligand.
3. The method of claim 1 , wherein the ligand comprises a scorpionate ligand.
4. The method of claim 1 , wherein the ligand comprises a substituted or unsubstituted trispyrazoylborate ligand.
5. The method of claim 1 , wherein the ligand comprises a tris(3,5-dimethyl-1-pyrazolyl)borate, tris(3,5-diethyl-1-pyrazolyl)borate, tris(3,5-dipropyl-1-pyrazolyl)borate, tris(3,5-diisopropyl-1-pyrazolyl)borate, tris(3,5-dibutyl-1-pyrazolyl)borate, tris(3,5-di(iso, sec, or tert)butyl-1-pyrazolyl)borate, or tris(1-pyrazolyl)borate ligand substituted with one or more substituents chosen from hydrogen, halogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, or aryl ligand.
6. The method of claim 1 , wherein the catalyst system comprises the nickel catalyst and it comprises:
wherein each R 3 and R 4 are independently selected from H, alkyl, alkenyl, cycloalkyl, cycloalkenyl, or aryl.
7. The method of claim 6 , wherein the catalyst comprises:
8. The method of claim 1 , wherein catalyst system comprise the copper catalyst and it comprises:
9. The method of claim 1 , wherein nickel, copper, and zinc catalyst have the formula:
wherein M is Ni, Cu, or Zn; and
R 5 and R 6 are independently selected from H, alkyl, alkenyl, cycloalkyl, cycloalkenyl, and aryl.
10. The method of claim 9 , wherein each R 5 and R 6 are independently selected from methyl, ethyl, iso-propyl, sec-butyl, and tert-butyl.
11. The method of claim 9 , wherein R 5 and/or R 6 are independently selected from di- or tri-alkyl substituted aryl.
12. The method of claim 1 , wherein the iridium catalyst comprises:
wherein
E is C or N;
X is halogen or other neutral ligand; and
R 1 and R 2 are independently selected from H, alkyl, alkenyl, cycloalkyl, cycloalkenyl, or aryl.
13. The method of claim 1 , wherein the iridium catalyst comprises:
14. The method of claim 1 , wherein the reactant is contacted with the catalyst system at a temperature of from 100° C. to 500° C., from 0.01 hour to 100 hours, at from 1 atm to 10 atm.
15. The method of claim 1 , wherein the 1-butanol selectivity is 80% or more and the 1-butanol yield is 20% or more.
16. A catalyst system for producing 1-butanol, comprising:
an iridium catalyst; and
a nickel catalyst comprising nickel, hydroxide, and a ligand, a copper catalyst comprising copper, hydroxide, and a ligand, or a zinc catalyst comprising zinc, hydroxide, and a ligand.
17. The catalyst system of claim 16 , wherein the ligand comprises a tripodal ligand.
18. The catalyst system of claim 16 , wherein the ligand comprises a scorpionate ligand.
19. The catalyst system of claim 16 , wherein the ligand comprises a substituted or unsubstituted trispyrazoylborate ligand.
20. The catalyst system of claim 16 , wherein the ligand comprises a tris(3,5-dimethyl-1-pyrazolyl)borate, tris(3,5-diethyl-1-pyrazolyl)borate, tris(3,5-dipropyl-1-pyrazolyl)borate, tris(3,5-diisopropyl-1-pyrazolyl)borate, tris(3,5-dibutyl-1-pyrazolyl)borate, tris(3,5-di(iso, sec, or tert)butyl-1-pyrazolyl)borate, or tris(1-pyrazolyl)borate ligand substituted with one or more substituents chosen from hydrogen, halogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, or aryl ligand.
21. The catalyst system of claim 16 , wherein the system comprises the nickel catalyst and the nickel catalyst comprises:
wherein each R 3 and R 4 are independently selected from H, alkyl, alkenyl, cycloalkyl, cycloalkenyl, or aryl.
22. The catalyst system of claim 21 , wherein the nickel catalyst comprises:
23. The catalyst system of claim 16 , wherein the system comprises the copper catalyst and the copper catalyst comprises:
24. The catalyst system of claim 16 , wherein nickel, copper, and zinc catalyst have the formula:
wherein M is Ni, Cu, or Zn; and
R 5 and R 6 are independently selected from H, alkyl, alkenyl, cycloalkyl, cycloalkenyl, and aryl.
25. The catalyst system of claim 24 , wherein each R 5 and R 6 are independently selected from methyl, ethyl, iso-propyl, sec-butyl, and tert-butyl.
26. The catalyst system of claim 24 , wherein R 5 and/or R 6 are independently selected from di- or tri-alkyl substituted aryl.
27. The catalyst system of claim 16 , wherein the iridium catalyst comprises:
wherein
E is C or N;
X is halogen or other neutral ligand; and
R 1 and R 2 are independently selected from H, alkyl, alkenyl, cycloalkyl, cycloalkenyl, or aryl.
28. The catalyst system of claim 16 , wherein the iridium catalyst comprises: