Compositions and methods for hydrocarbon functionalization

• US 10,450,259 B2
• Filed: 08/31/2018
• Issued: 10/22/2019
• Est. Priority Date: 06/26/2013
• Status: Active Grant

• Current Assignee: The Trustees of Princeton University (Princeton University), University of Virginia Patent Foundation (University of Virginia)
• Original Assignee: University of Virginia Patent Foundation (University of Virginia)
• Inventors: Gunnoe, Thomas Brent, Fortman, George, Boaz, Nicholas C., Groves, John T.
• Primary Examiner(s): Cutliff, Yate' K
• Application Number:
  US16/119,125
• Publication Number:
  US 20190062255A1
• Time in Patent Office: 417 Days
• CPC Class Codes: B01J 19/123 Ultraviolet light
• CPC Class Codes: B01J 19/127 Sunlight; Visible light
• CPC Class Codes: B01J 19/24 Stationary reactors without moving elements inside B01J19/08, B01J19/26 take precedence; with stationary particles B01J8/02
• CPC Class Codes: B01J 2219/00051 Controlling the temperature
• CPC Class Codes: B01J 2219/00162 controlling the pressure
• CPC Class Codes: B01J 2219/1278 Time
• CPC Class Codes: B01J 2219/24 Stationary reactors without moving elements inside
• CPC Class Codes: C07C 17/00 Preparation of halogenated hydrocarbons
• CPC Class Codes: C07C 19/00 Acyclic saturated compounds containing halogen atoms
• CPC Class Codes: C07C 19/03 Chloromethanes
• CPC Class Codes: C07C 19/043 Chloroethanes
• CPC Class Codes: C07C 2602/42 the bicyclo ring system containing seven carbon atoms
• CPC Class Codes: C07C 2603/74 Adamantanes
• CPC Class Codes: C07C 29/00 Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
• CPC Class Codes: C07C 29/03 by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by simultaneous introduction of -OH groups and halogens C07C29/64
• CPC Class Codes: C07C 29/147 of carboxylic acids or derivatives thereof
• CPC Class Codes: C07C 29/48 by oxidation reactions with formation of hydroxy groups
• CPC Class Codes: C07C 31/04 Methanol
• CPC Class Codes: C07C 31/08 Ethanol
• CPC Class Codes: C07C 31/10 containing three carbon atoms
• CPC Class Codes: C07C 67/035 : by reacting carboxylic acids or symmetrical anhydrides with saturated hydrocarbons
• CPC Class Codes: C07C 69/14 : of monohydroxylic compounds
• CPC Class Codes: C07C 69/63 : of saturated acids
• CPC Class Codes: C10L 1/02 : essentially based on components consisting of carbon, hydrogen, and oxygen only

Abstract

Embodiments of the present disclosure provide for methods of hydrocarbon functionalization, methods and systems for converting a hydrocarbon into a compound including at least one group ((e.g., hydroxyl group) (e.g., methane to methanol)), functionalized hydrocarbons, and the like. Systems and methods as described herein can utilize photocatalysis.

Claims

1. A method, comprising:

mixing A_aX_n, an iodine-based compound, and a source of functionalization to form a first mixture, wherein A is selected from the group consisting of;

hydrogen, lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, transition metals, aluminum, gallium, thallium, indium, tin, sulfur, ammonium (NH₄⁺), alkylammonium, phosphonium (PH₄⁺), alkylphosphonium, arylphosphonium, or trimethyl sulfonium ([S(CH₃)₃]⁺) and a combination thereof, wherein X is chlorine or bromine, wherein subscript “

a”

is an oxidation state of X and subscript “

n”

is an oxidation state of A;

mixing the first mixture with a hydrocarbon in the gas phase to form a second mixture; and

applying light from a light source to the second mixture to make a functionalized hydrocarbon.

2. The method of claim 1, further comprising:

converting the functionalized hydrocarbon to a compound including at least one group selected from the group consisting of;

hydroxyl, halide, carbonyl, and a combination thereof.

3. The method of claim 2, wherein the compound is selected from an alcohol or glycol.

4. The method of claim 2, wherein the compound is methanol, ethanol, or propanol.

5. The method of claim 1, wherein the hydrocarbon is selected from the group consisting of:

methane, ethane, propane, butane, and a combination thereof.

6. The method of claim 1, wherein the hydrocarbon is aliphatic.

7. The method of claim 1, wherein the hydrocarbon is aromatic.

8. The method of claim 1, wherein A_aX_n is selected from the group consisting of:

HCl, NaCl, KCl, CaCl₂, LiCl, ZnCl₂, BeCl₂, MgCl₂, PCl₃, NH₄Cl, 0014, CHCl₃, transition metal chlorides, main group metal chlorides or organochlorides, or combination thereof.

9. The method of claim 1, wherein A is selected from the group consisting of:

hydrogen, lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, aluminum, gallium, thallium, indium, tin, sulfur, ammonium (NH₄⁺), alkylammonium, phosphonium (PH₄⁺), alkylphosphonium, arylphosphonium, or trimethyl sulfonium ([S(CH₃)₃]⁺) and a combination thereof.

10. The method of claim 1, wherein the iodine-based compound is selected from the group consisting of:

iodate, periodate, iodine oxide, iodosyl (IO⁺), trivalent iodine compound, and a combination thereof.

11. The method of claim 1, wherein the iodine-based compound is Q(IO₃)_p, wherein Q is selected from the group consisting of:

hydrogen, lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, transition metals, aluminum, gallium, thallium, indium, tin, sulfur, ammonium (NH₄⁺), alkylammonium, phosphonium (PH₄⁺), alkylphosphonium, arylphosphonium, and trimethyl sulfonium ([S(CH₃)₃]⁺), wherein “

p”

is 1 to 5.

12. The method of claim 1, wherein the iodine-based compound is selected from the group consisting of:

KIO₃, Ca(IO₃)₂, Ba(IO₃)₂, Cu(IO₃)₂, NH₄IO₃, H₅IO₆, KIO₄, NaIO₄ and NH₄IO₄, I(TFA)₃, I₂O₅, [IO]⁺, [IO₂]⁺, and combination thereof.

13. The method of claim 1, wherein the source of functionalization is selected from the group consisting of:

trifluoroacetic acid, trifluoroacetic anhydride, hexafluorobutyric acid, water, sulfuric acid, acetic acid, supercritical carbon dioxide, phosphoric acids, and a combination thereof.

14. The method of claim 1, wherein the light form the light source is applied to the second mixture for a period of time of about 24 hours to about 72 hours.

15. The method of claim 1, wherein mixing the first mixture with the hydrocarbon is conducted at an internal pressure of about 15 to 1500 psi and at a temperature of about 25 to 300°

C. for about 10 minutes to 5 days.

16. The method of claim 1, wherein A_aX_n is about 0.2 to 25 weight % of the first mixture, wherein the iodine-based compound is about 2 to 40 weight % of the first mixture, wherein the source of functionalization is about 30 to 95 weight % of the first mixture, and wherein the amount of the hydrocarbon relative to the first mixture is about 0.01 to 20 weight %.

17. The method of claim 1, wherein the mass of A_aX_n relative to the source of functionalization is about 0.14 to 10% and wherein the mass of the iodine-based compound relative to the source of functionalization is about 17 to 26%.

18. A system for producing a functionalized hydrocarbon, comprising:

a vessel including A_aX_n, an iodine-based compound, and a source of functionalization to form a first mixture and a hydrocarbon, wherein A is selected from the group consisting of;

hydrogen, lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, transition metals, aluminum, gallium, thallium, indium, tin, sulfur, ammonium (NH₄⁺), alkylammonium, phosphonium (PH₄⁺), alkylphosphonium, arylphosphonium, or trimethyl sulfonium ([S(CH₃)₃]⁺) and a combination thereof, wherein X is chlorine or bromine, wherein “

a”

is the oxidation state of X and “

n”

is the oxidation state of A;

wherein the vessel further comprises a light source.

19. The system of claim 18, wherein the light source is a mercury arc lamp or a compact fluorescent light bulb.

20. The system of claim 18, wherein the vessel further comprises a pressure system to pressurize the vessel to about 15 to 1500 psi, a heating system to heat the vessel to about 25 to 300°

C., or both.