Methods for selectively hydrogenating benzene with supported organometallic catalysts and systems and methods for reducing benzene in gasoline using such catalysts

1. A method for selectively hydrogenating benzene with a supported organocirconium hydrogenating catalyst, the method comprising the step of:

contacting an arene-containing reaction stream comprising benzene and one or more additional arenes with hydrogen in the presence of a supported organocirconium hydrogenating catalyst under reaction conditions effective to hydrogenate at least benzene in the arene-containing reaction stream to produce a reaction effluent having a ratio of benzene to additional arenes that is lower than the ratio of benzene to additional arenes in the arene-containing reaction stream;

wherein the supported organocirconium hydrogenating catalyst comprises a catalytically active organocirconium species and a Brønsted acidic sulfated metal oxide support,

wherein the catalytically active organozirconium species has the general formula Cp # c ZrR r ,

where Cp # is a cyclopentadienyl ligand selected from the group consisting of cyclopentadienyl (Cp), pentamethylcyclopentadienyl (Cp*), a cyclopentadienyl radical substituted with alkyl or trimethylsilyl groups, and a fused cycolopentadienyl radical;

c is from 0 to 2;

R is a ligand selected from the group consisting of benzyl or substituted benzyl (Bz), phenyl or substituted phenyl(Ph), 2,2-dimethylpropyl or substituted 2,2-dimethylpropyl, trimethylsilylmethyl (neosilyl) or substituted trimethylsilymethyl, and 2,2-dimethylethylbenzyl (neophyl) or substituted 2,2-dimethylethylbenzyl;

and r is determined the equation r=3−c, wherein benzene hydrogenation takes place with a Michaelis-Menten constant (K m ) of less than 500 and with a benzene TOF of greater than 100 mol (mol Zr) −1 h −1 .

2. The method of claim 1 , wherein the one or more additional arenes in the arene-containing reaction stream includes one or more arenes selected from the group consisting of toluene, ethyl benzene, xylenes, mesitylene, A9 aromatics and A10 aromatics.

3. The method of claim 1 , wherein the one or more additional arenes in the arene-containing reaction stream includes toluene.

4. The method of claim 1 , wherein the catalytically active organozirconium species has the formula Cp*ZrBz 2 , where Bz is a benzyl ligand or substituted benzyl ligand, and wherein the Brønsted acidic sulfated metal oxide support is sulfated zirconia (ZrS).

5. The method of claim 1 , wherein the arene-containing reaction stream comprises from about 1 to about 10 wt % benzene.

6. The method claim 1 , wherein the Brønsted acidic sulfated metal oxide support is selected from the group consisting of sulfated alumina (AlS), sulfated zirconia (ZrS), sulfated titania (TiS), sulfated hafnia (HfS), sulfated iron oxide (FeS), sulfated tin oxide (TnS), tungstated zirconia (ZrW), and combinations thereof.

7. The method of claim 1 , wherein the arene-containing reaction stream comprises from about 1 to about 10 wt % benzene and from about 15 to about 30 wt % toluene.

8. The method of claim 1 , wherein the arene-containing reaction stream comprises from about 40 to about 55 wt % total arenes.

9. The method of claim 1 , wherein the supported organozirconium hydrogenating catalyst promotes benzene catalytic hydrogenation at a rate that is at least 25% higher than the rate of catalytic hydrogenation of any other arene present in the arene-containing reaction stream.

10. A method for reducing benzene content in an arene-containing reaction stream, the method comprising the step of:

contacting an arene-containing reaction stream comprising benzene and one or more additional arenes with hydrogen in the presence of a supported organozirconium hydrogenating catalyst under reaction conditions effectve to hydrogenate benzene in the arene-containing reaction stream to produce an effluent having a ratio of benzene to additional arenes in the effluent that is lower than the ratio of benzene to additional arenes in the arene-containing reaction stream,

wherein the arene-containing reaction stream comprises a refinery stream, and the supported organozirconium hydrogenating catalyst comprises a catalytically active organozirconium species and a Brønsted acidic sulfated metal oxide support,

wherein the catalytically active organozirconium species has the general formula Cp # c ZrR r .

where Cp # is a cyclopentadienyl ligand selected from the group consisting of cyclopentadienyl (Cp), pentamethylcyclopentadienyl (Cp*), a cyclopentadienyl radical substituted with alkyl or trimethylsilyl groups, and a fused cyclopentadienyl radical;

c is from 0 to 2;

Zr is zirconium;

R is a ligand selected from the group comsisting of benzyl or substituted benzyl (Bz), phenyl or substituted phenyl (Ph), 2,2-dimethylpropyl or substituted 2,2-dimethylpropyl, trimethylsilylmethyl (neosilyl) or substituted trimethylsilymethyl, and 2,2-dimethylethylbenzyl (neophyl) or substituted 2,2-dimethylethylbenzyl;

and r is determined by the equation r=3−c, wherein benzene hydrogenation takes place with a Michaelis-Menten constant (K m ) of less than 500 and with a benzene TOF of greater than 100 mol (mol Zr) −1 h −1 .

11. The method of claim 10 , wherein the catalytically active organozirconium species has the formula Cp*ZrBz 2 , where Bz is a benzyl ligand or substituted benzyl ligand, and wherein the Brønsted acidic sulfated metal oxide support is sulfated zirconia (ZrS).

12. The method of claim 10 , wherein the refinery stream comprises from about 1 to about 10 wt % benzene.

13. The method of claim 10 , wherein the Brønsted acidic sulfated metal oxide support is selected from the group consisting of sulfated alumina (AlS), sulfated zirconia (ZrS), sulfated titania (TiS), sulfated hafnia (HfS), sulfated iron oxide (FeS), sulfated tin oxide (TnS), tungstated zirconia (ZrW), and combinations thereof.

14. The method of claim 10 , wherein the arene-contianing reaction stream comprises from about 1 to about 10 wt % benzene and from about 15 to about 30 wt % toluene.

15. The method of claim 10 , wherein the supported organozirconium hydrogenating catalyst promotes benzene catalytic hydrogenation at a rate that is at least 25% higher than the rate of catalytic hydrogenation of any other arene present in the arene-containing reaction stream.

16. A method for selectively hydrogenating benzene with a supported organozirconium hydrogenating catalyst, the method comprising the step of:

contacting an arene-containing reaction stream comprising benzene and one or more additional arenes with hydrogen in the presence of a supported organozirconium hydrogenating catalyst under reaction conditions effective to hydrogenate at least benzene in the arene-containing reaction stream to produce a reaction effluent having a ratio of benzene to additional arenes that is lower than the ratio of benzene to additional arenes in the arene-containing reaction stream;

wherein the supported organozirconium hydrogenating catalyst comprises a catalytically active organozirconium species and a Brønsted acidic sulfated metal oxide support,

wherein the catalytically active organozirconium species has the general formula Cp*ZrR 2 .

where Cp* is pentamethylcyclopentadienyl and R is a ligand selected from the group consisting of benzyl or substituted benzyl (Bz); and

wherein the supported organozirconium hydrogenating catalyst promotes benzene catalytic hydrogenation at a rate that is at least 25% higher than the rate of catalytic hydrogenation of any other arene present in the arene-contianing reaction stream.

17. The method of claim 16 , wherein the Brønsted acidic sulfated metal oxide support is selected from the group consisting of sulfated alumina (AlS), sulfated zirconia (ZrS), sulfated titania (TiS), sulfated hafnia (HfS), sulfated iron oxide (FeS), sulfated tin oxide (TnS), tungstated zirconia (ZrW), and combinations thereof.

18. The method of claim 16 , wherein the arene-containing reaction stream comprises from about 1 to about 10 wt % benzene and from about 15 to about 30 wt % toluene.

19. The method of claim 16 , wherein the one or more additional arenes in the arene-containing reaction stream includes one or more arenes selected from the group consisting of toluene, ethyl benzene, xylenes, mesitylene, A9 aromatics and A10 aromatics.

20. The method of claim 16 , wherein benzene hydrogenation takes place with a Michaelis-Menten constant (K m ) of less than 500 and with a benzene TOF of greater than 100 mol (mol Zr) −1 h −1 .