Chromium-catalyzed production of alcohols from hydrocarbons in the presence of oxygen
Processes for converting a hydrocarbon reactant into an alcohol compound and/or a carbonyl compound are disclosed in which the hydrocarbon reactant and either a supported chromium (VI) catalyst or a supported chromium (II) catalyst are contacted, optionally with UV-visible light irradiation, followed by exposure to an oxidizing atmosphere and then hydrolysis to form a reaction product containing the alcohol compound and/or the carbonyl compound. The presence of oxygen significant increases the amount of alcohol/carbonyl product formed, as well as the formation of oxygenated dimers and trimers of certain hydrocarbon reactants.
1. A supported chromium complex having formula (A):
wherein:
each X independently is Si, Ti, Al, P, B, or Zr; and
R is a C 1 to C 36 hydrocarbyl group; or
a supported chromium complex having formula (B):
wherein:
each X independently is Si, Ti, Al, P, B, or Zr;
Y is nothing, H 2 O, a C 1 to C 36 alcohol group, or a C 2 to C 36 ketone group;
R is H or a C 1 to C 36 hydrocarbyl group; and
n is an integer from 0 to 10; or
a supported chromium complex having formula (C):
wherein:
each X independently is Si, Ti, Al, P, B, or Zr;
Y is a —OR, —R, a C 1 to C 36 alcohol group, or a C 2 to C 36 ketone group; and
R is a C 1 to C 36 hydrocarbyl group; or
a supported chromium complex having formula (D):
wherein:
each X independently is Si, Ti, Al, P, B, or Zr;
R is H or a C 1 to C 36 hydrocarbyl group; and
n is an integer from 0 to 10.
2. The supported chromium complex of claim 1 , wherein each X independently is Si, Ti, or Al.
3. The supported chromium complex of claim 1 , wherein R is a C 1 to C 18 hydrocarbyl group.
4. The supported chromium complex of claim 1 , wherein R is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, or an octadecyl group.
5. The supported chromium complex of claim 1 , wherein the supported chromium complex has formula (A).
6. The supported chromium complex of claim 1 , wherein the supported chromium complex has formula (B).
7. The supported chromium complex of claim 1 , wherein the supported chromium complex has formula (C).
8. The supported chromium complex of claim 1 , wherein the supported chromium complex has formula (D).