Hydrocarbon synthesis
View Patent ↗A method of synthesizing hydrocarbons from smaller hydrocarbons includes the steps of hydrocarbon halogenation, simultaneous oligomerization and hydrogen halide neutralization, and product recovery, with a metal-oxygen cataloreactant used to facilitate carbon-carbon coupling. Treatment with air or oxygen liberates halogen and regenerates the cataloreactant.
1. A method of making a product hydrocarbon having a carbon number C n , where n>2, comprising:
reacting a halogenating agent with a reactant hydrocarbon having a carbon number C m , where m<n, to form a halogenated hydrocarbon;
contacting the halogenated hydrocarbon with a first solid metal-oxygen cataloreactant to form a hydrogen halide and a plurality of product hydrocarbons having a carbon number C n , where n>2;
contacting the hydrogen halide with a second solid metal-oxygen cataloreactant to form a halogenated cataloreactant;
recovering the product hydrocarbons; and
contacting the halogenated cataloreactant with oxygen or air to regenerate the cataloreactant and form a molecular halogen.
2. The method of claim 1 further comprising:
recycling the molecular halogen as the halogenating agent to react with the reactant hydrocarbon.
3. The method of claim 1 wherein the first solid cataloreactant and the second solid cataloreactant are the same solid cataloreactant.
4. The method of claim 1 wherein the first solid cataloreactant or the second solid cataloreactant is a zeolite doped with an alkaline-earth metal.
5. The method of claim 4 wherein the zeolite has an Si:Al ratio of from about 80:1 to 280:1.
6. The method of claim 4 wherein the zeolite has an Si:Al ratio of about 80:1.
7. The method of claim 4 wherein the zeolite has an Si:Al ratio of about 280:1.
8. The method of claim 4 wherein the zeolite doped with an alkaline-earth metal has an alkaline earth metal:silicon ratio of about 4:1.
9. The method of claim 1 wherein the product hydrocarbons comprise at least one aromatic hydrocarbon.
10. The method of claim 9 wherein the at least one aromatic hydrocarbon comprises at least one hydrocarbon selected from the group consisting of benzene, toluene, xylene, ethylbenzene, mesitylene, and ethylmethylbenzene.
11. The method of claim 1 wherein the product hydrocarbons comprise at least one branched alkane.
12. The method of claim 1 wherein the product hydrocarbons comprise at least one olefin.
13. The method of claim 1 wherein the product hydrocarbons comprise at least one alkane, at least one olefin, and at least one aromatic hydrocarbon.
14. The method of claim 1 wherein the product hydrocarbons comprise a gasoline grade mixture of hydrocarbons.
15. The method of claim 1 further comprising allowing any C 1 to C 3 hydrocarbons, which are formed from allowing the halogenated hydrocarbon to contact the first solid metal-oxygen cataloreactant, to contact the first solid metal-oxygen cataloreactant again to form one or more C 4 or higher hydrocarbons.
16. The method of claim 15 wherein at least a portion of the C 1 to C 3 hydrocarbons comprise at least one olefin.
17. The method of claim 1 wherein the halogenating agent comprises bromine.
18. The method of claim 1 wherein the first solid metal-oxygen cataloreactant is contacted with the halogenated hydrocarbon in a fixed bed.
19. The method of claim 1 wherein the second solid metal-oxygen cataloreactant is contacted with the hydrogen halide in a fixed bed.
20. The method of claim 1 wherein the first solid metal-oxygen cataloreactant is contacted with the halogenated hydrocarbon in a fluidized bed.
21. The method of claim 1 wherein the second solid metal-oxygen cataloreactant is contacted with the hydrogen halide in a fluidized bed.
22. A method of making a product hydrocarbon having a carbon number C n , where n>2, comprising:
reacting a halogenating agent with a reactant hydrocarbon having a carbon number C m , where m<n, to form a halogenated hydrocarbon;
contacting the halogenated hydrocarbon with a first solid metal-oxygen cataloreactant to form a hydrogen halide and a plurality of product hydrocarbons having a carbon number C n , where n>2, at least 50% of which are C 6 or higher hydrocarbons;
contacting the hydrogen halide with a second solid metal-oxygen cataloreactant to form a halogenated cataloreactant;
recovering the product hydrocarbons; and
contacting the halogenated cataloreactant with oxygen or air to regenerate the cataloreactant and form a molecular halogen.
23. The method of claim 22 wherein the first solid cataloreactant and the second solid cataloreactant are the same solid cataloreactant.
24. A method of making a product hydrocarbon having a carbon number C n , where n>2, comprising:
reacting a halogenating agent with a reactant hydrocarbon having a carbon number C m , where m<n, to form a halogenated hydrocarbon;
contacting the halogenated hydrocarbon with a first solid metal-oxygen cataloreactant to form a hydrogen halide and a plurality of product hydrocarbons having a carbon number C n , where n>2, at least 70% of which are C 5 or higher hydrocarbons;
contacting the hydrogen halide with a second solid metal-oxygen cataloreactant to form a halogenated cataloreactant;
recovering the product hydrocarbons; and
contacting the halogenated cataloreactant with oxygen or air to regenerate the cataloreactant and form a molecular halogen.
25. The method of claim 24 wherein the first solid cataloreactant and the second solid cataloreactant are the same solid cataloreactant.
26. A method of making a product hydrocarbon having a carbon number C n , where n>2, comprising:
reacting a halogenating agent with a reactant hydrocarbon having a carbon number C m , where m<n, to form a halogenated hydrocarbon;
contacting the halogenated hydrocarbon with a first solid metal-oxygen cataloreactant to form a hydrogen halide and a plurality of product hydrocarbons having a carbon number C n , where n>2, at least 50% of which are C 6 or higher hydrocarbons, and at least 70% of which are C 5 or higher hydrocarbons;
contacting the hydrogen halide with a second solid metal-oxygen cataloreactant to form a halogenated cataloreactant;
recovering the product hydrocarbons; and
contacting the halogenated cataloreactant with oxygen or air to regenerate the cataloreactant and form a molecular halogen.
27. The method of claim 26 wherein the first solid cataloreactant and the second solid cataloreactant are the same solid cataloreactant.