Process for the deep desulfurization of heavy pyrolysis gasoline
View Patent ↗A process for the deep desulfurization of a heavy pyrolysis gasoline to very low levels of organic sulfur, e.g., 30 ppmv or less, with minimal octane number loss through aromatics saturation. The deep desulfurization is accomplished by contacting the heavy pyrolysis gasoline feedstock, partially in liquid and partially in gaseous phase, with a hydrogen treat gas containing a minimum H 2 S level in the presence of a hydrogenation catalyst in a one or two reactor system operated in trickle flow, using a low temperature, moderate pressure operating condition.
1. A process for the deep desulfurization of a heavy pyrolysis gasoline feedstock containing a diolefin concentration, an organic sulfur concentration and a high aromatic concentration, wherein said process comprises:
heating said heavy pyrolysis gasoline feedstock to a temperature sufficient to provide a heated pyrolysis gasoline feedstock having a substantial portion that is in a gaseous phase and another substantial portion that is in a liquid phase;
introducing said heated pyrolysis gasoline feedstock that is in said liquid phase and said gaseous phase into a reactor vessel, or more than one reactor vessel in series flow arrangement, that contains a hydrogenation catalyst and is operated in a downflow mode;
contacting said heated pyrolysis gasoline feedstock in the presence of an added hydrogen treat gas having an H 2 S concentration of at least 100 ppmv with said hydrogenation catalyst at a moderate temperature condition effective to selectively hydrogenate a substantial portion of the diolefins contained in said heated pyrolysis gasoline feedstock to monoolefins and a substantial portion of the organic sulfur in said heated pyrolysis gasoline feedstock to H 2 S, but not at a temperature to significantly hydrogenate the aromatic compounds contained in said heated pyrolysis gasoline feedstock;
yielding from said reactor vessel, or more than one reactor vessel in series flow arrangement, a reactor effluent; and
separating H 2 S and unreacted hydrogen from said reactor effluent and recovering from said reactor effluent a low-sulfur pyrolysis gasoline product that contains less than 30 ppm organic sulfur compounds.
2. A process as recited in claim 1 , wherein said substantial portion of said heated pyrolysis gasoline feedstock that is in said gaseous phase is in the range of from 10 wt % to 80 wt % of said heated pyrolysis gasoline feedstock and said another substantial portion of said heated pyrolysis gasoline feedstock that is in said liquid phase is in the range of from 20 wt % to 90 wt % of said heated pyrolysis gasoline feedstock.
3. A process as recited in claim 2 , wherein said moderate temperature condition includes a contacting temperature in the range of from 175° C. to 275° C., and wherein said reactor vessel is operated at an operating pressure in the range of from 400 psig to 800 psig.
4. A process as recited in claim 3 , further comprising: discontinuing the contacting of said heated pyrolysis gasoline feedstock with said hydrogenation catalyst; and, thereafter, contacting said hydrogenation catalyst with a hot hydrogen stream comprising hydrogen and a concentration of H 2 S of at least 400 ppmv at a hydrogen treatment temperature of at least 370° C. and for a treatment period sufficient to remove gum deposits and fouling material from said hydrogenation catalyst and to restore at least a portion of lost catalyst activity of said hydrogenation catalyst.
5. A process as recited in claim 4 , wherein said diolefin concentration is in the range of from 100 ppmw to 3 wt % of said heavy pyrolysis gasoline feedstock, said organic sulfur concentration is in the range of from 75 ppmw to 2,000 ppmw; and said high aromatics concentration is in the range of from 30 wt % to 85 wt % of the total weight of said heavy pyrolysis gasoline feedstock.
6. A process as recited in claim 5 , wherein said hydrogenation catalyst comprises molybdenum and either cobalt or nickel, or both, supported on an inorganic oxide support.
7. A process as recited in claim 6 , wherein said low-sulfur pyrolysis gasoline product has a concentration of diolefins of less than 75 ppmw.
8. A process as recited in claim 7 , wherein said reactor vessel includes said more than one reactor vessel in series flow arrangement which includes a first reactor vessel that contains a first hydrogenation catalyst and that is operated in said downflow mode and a second reactor vessel that contains a second hydrogenation catalyst and that is operated in said downflow mode, wherein said process comprises:
contacting said heated pyrolysis gasoline feedstock in the presence of said added hydrogen treat gas with said first hydrogenation catalyst at said moderate temperature condition and yielding from said first reactor vessel a first reactor effluent;
contacting said first reactor effluent in the presence of said added hydrogen treat gas with said second hydrogenation catalyst at a desulfurization condition effective to hydrogenate a substantial portion of the organic sulfur compounds contained in said first reactor effluent to H 2 S, but not at a temperature to significantly hydrogenate the aromatic compounds contained in said first reactor effluent; and
yielding from said second reactor vessel a second reactor effluent as said reactor effluent.
9. A process as recited in claim 8 , wherein said heavy pyrolysis gasoline feedstock has been previously hydrogenated to selectively convert diolefins and alkenyl aromatics to mono olefins and alkyl aromatics.
10. The process of claim 9 , wherein the heavy pyrolysis gasoline feedstock is heated in a steam heat exchanger.
11. The process of claim 10 , wherein the reactor vessel contains a fixed catalyst bed equipped with a high dispersion tray to uniformly distribute the pyrolysis gasoline feedstock across the top of the fixed catalyst bed.