Compositions and methods for hydrocarbon functionalization
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.
1. A method, comprising:
mixing A a X 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 (NH 4 + ), alkylammonium, phosphonium (PH 4 + ), alkylphosphonium, arylphosphonium, or trimethyl sulfonium ([S(CH 3 ) 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; and
mixing the first mixture with a hydrocarbon in the gas phase 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 a X n is selected from the group consisting of: HCl, NaCl, KCl, CaCl 2 , LiCl, ZnCl 2 , BeCl 2 , MgCl 2 , PCl 3 , NH 4 Cl, CCl 4 , CHCl 3 , transition metal chlorides, main group metal chlorides or organochlorides, or combination thereof.
9. 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.
10. The method of claim 1 , wherein the iodine-based compound is Q(IO 3 ) 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 (NH 4 + ), alkylammonium, phosphonium (PH 4 + ), alkylphosphonium, arylphosphonium, and trimethyl sulfonium ([S(CH 3 ) 3 ] + ), wherein “p” is 1 to 5.
11. The method of claim 1 , wherein the iodine-based compound is selected from the group consisting of: KIO 3 , Ca(IO 3 ) 2 , Ba(IO 3 ) 2 , Cu(IO 3 ) 2 , NH 4 IO 3 , H 5 IO 6 , KIO 4 , NaIO 4 and NH 4 IO 4 , I(TFA) 3 , I 2 O 5 , [IO] + , [IO 2 ] + , and combination thereof.
12. 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.
13. 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.
14. The method of claim 1 , wherein A a X 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 %.
15. The method of claim 1 , wherein the mass of A a X 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%.
16. A system for producing a functionalized hydrocarbon, comprising:
a vessel including A a X 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 (NH 4 + ), alkylammonium, phosphonium (PH 4 + ), alkylphosphonium, arylphosphonium, or trimethyl sulfonium ([S(CH 3 ) 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 includes a pressure system to pressurize the vessel to about 15 to 1500 psi and a heating system to heat the vessel to about 25 to 300° C.
17. 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 (NH 4 + ), alkylammonium, phosphonium (PH 4 + ), alkylphosphonium, arylphosphonium, or trimethyl sulfonium ([S(CH 3 ) 3 ] + ) and a combination thereof.