Mineral oils: processes and products – Refining – Sulfur removal
Reexamination Certificate
2001-12-19
2003-04-08
Langel, Wayne A. (Department: 1754)
Mineral oils: processes and products
Refining
Sulfur removal
C208S20800M, C208S209000, C208S213000, C208S299000, C208S305000, C585S820000, C585S823000, C585S826000, C502S038000, C502S041000, C502S052000
Reexamination Certificate
active
06544410
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to the removal of sulfur from sulfur-containing fluid streams such as cracked-gasolines and diesel fuels. In another aspect, this invention relates to the regeneration of a sorbent composition which is used to desulfurize a sulfur-containing fluid.
Hydrocarbon-containing fluids such as gasoline and diesel fuels typically contain a quantity of sulfur. High levels of sulfur in such automotive fuels is undesirable because oxides of sulfur present in automotive exhaust may irreversibly poison noble metal catalysts employed in automobile catalytic converters. Emissions from such poisoned catalytic converters may contain high levels of non-combusted hydrocarbons, oxides of nitrogen, and/or carbon monoxide, which, when catalyzed by sunlight, form ground level ozone, more commonly referred to as smog.
Much of the sulfur present in the final blend of most gasolines originates from a gasoline blending component commonly known as “cracked-gasoline.” Thus, reduction of sulfur levels in cracked-gasoline will inherently serve to reduce sulfur levels in most gasolines, such as, automobile gasolines, racing gasolines, aviation gasolines, boat gasolines, and the like.
Many conventional processes exist for removing sulfur from cracked-gasoline. However, most conventional sulfur removal processes, such as hydrodesulfurization, tend to saturate olefins and aromatics in the cracked-gasoline and thereby reduced its octane number (both research and motor octane number). Thus, there is a need for a process wherein desulfurization of cracked-gasoline is achieved while the octane number is maintained.
In addition to the need for removing sulfur from cracked-gasoline, there is also a need to reduce sulfur content in diesel fuel. In removing sulfur from diesel fuel by conventional hydrodesulfurization, the cetane is improved but there is a large cost in hydrogen consumption. Such hydrogen is consumed by both hydrodesulfurization and aromatic hydrogenation reactions. Thus, there is a need for a process wherein desulfurization of diesel fuel is achieved without significant consumption of hydrogen so as to provide a more economical desulfurization process.
To satisfy such needs, there has been developed a process for desulfurizing hydrocarbon-containing fluids such as cracked-gasolines, diesel fuels, or other refinery streams (e.g., naphtha, alkylate, isomerate, reformate, distillate, and the like) wherein a sorbent comprising zinc oxide is contacted with the sulfur-containing fluid stream under conditions sufficient to remove at least a portion of the sulfur from the fluid stream and provide a sulfurized sorbent comprising zinc sulfide. The sulfurized sorbent is thereafter contacted with an oxygen-containing regeneration stream under conditions sufficient to convert at least a portion of the zinc sulfide to zinc oxide, thereby providing a regenerated sorbent. The regenerated sorbent can then be contacted with a reducing stream to provide an activated sorbent. Thereafter, the activated sorbent can, once again, be contacted with the sulfur-containing fluid stream.
During the regeneration step of such a desulfurization process, certain regeneration conditions can cause sulfates to form on/in the sorbent composition. Such sulfation of the sorbent is undesirable for a number of reasons. For example, the presence of excess sulfates on/in the sorbent reduces the sulfur-loading capabilities of the sorbent and thereby effectively deactivates the sorbent. Further, once an excessive amount of sulfates has formed on/in the sorbent, it can be difficult to remove the sulfates from the sorbent under conventional regeneration and activation conditions.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide an improved process for regenerating a sorbent composition while minimizing sulfation of the sorbent.
Another object of the present invention is to provide a desulfurization process which extends the useful life of a sorbent composition by employing a unique process for regenerating the sorbent.
It should be noted that the above-listed objects need not all be accomplished by the invention claimed herein and other objects and advantages of the invention will be apparent from the following description of the invention and the appended claims.
In one aspect of the invention, a process for regenerating a sorbent is provided. The process comprises, consists essentially of, or consists of the steps of: (a) charging an oxygen-containing regeneration stream comprising less than 10 mole percent sulfur dioxide to a regeneration zone; (b) charging a sulfurized sorbent comprising a promoter metal and zinc sulfide to the regeneration zone; and (c) contacting the sulfurized sorbent with the regeneration stream in the regeneration zone under regeneration conditions sufficient to maintain an average sulfur dioxide partial pressure in the regeneration zone of from about 0.1 to about 10 psig.
In accordance with another aspect of the present invention, there is provided a sorbent regeneration and activation process comprising, consisting essentially of, or consisting of the steps of: (a) contacting a sulfurized sorbent comprising zinc sulfide with an oxygen-containing stream in a regeneration zone under regeneration conditions sufficient to maintain an average sulfur dioxide partial pressure in the regeneration zone of from about 0.1 to about 10 psig, thereby providing a desulfurized sorbent; and (b) contacting the desulfurized sorbent with a reducing stream in an activation zone maintained at a temperature which is more than about 300 and less than about 1,000° F., thereby providing an activated sorbent.
In accordance with a further aspect of the present invention, there is provided a desulfurization process comprising, consisting essentially of, or consisting of the steps of: (a) contacting a sulfurized sorbent comprising a promoter metal and zinc sulfide with an oxygen-containing stream in a regeneration zone under regeneration conditions sufficient to convert at least a portion of the zinc sulfide to zinc oxide, thereby providing a desulfurized sorbent, the regeneration conditions including an average sulfur dioxide partial pressure of from about 0.1 to about 10 psig; (b) contacting at least a portion of the desulfurized sorbent with a hydrogen-containing stream in an activation zone under activation conditions sufficient to reduce the valence of the promoter metal, thereby providing an activated sorbent; and (c) contacting at least a portion of the activated sorbent with a sulfur-containing fluid comprising at least about 50 ppmw sulfur in a desulfurization zone under desulfurization conditions sufficient to provide a desulfurized fluid comprising less than about 50 weight percent of the amount of sulfur in the sulfur-containing fluid, wherein at least about 50 weight percent of the sulfur in the sulfur-containing fluid is present in the form of organosulfur compounds.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with one embodiment of the present invention, a novel process is provided for desulfurizing a sulfur-containing fluid by contacting the sulfur-containing fluid with a sorbent and thereafter regenerating and activating or re-activating the sorbent.
The sulfur-containing fluid employed in the process of the present invention is preferably a hydrocarbon-containing fluid comprising a quantity of sulfur compounds therein. Preferably, such hydrocarbon-containing fluid can be used as a fuel or can be a precursor to fuel. Examples of suitable hydrocarbon-containing fluids include cracked-gasoline, diesel fuels, jet fuels, straight-run naphtha, straight-run distillates, coker gas oil, coker naphtha, alkylates, crude oil, light cycle oil, and straight-run gas oil. Most preferably, the sulfur-containing fluid comprises a hydrocarbon-containing fluid selected from the group consisting of gasoline, cracked-gasoline, diesel fuel, and mixtures thereof.
As used herein, the term “gasoline” denotes a mixture of hydrocarbons boiling in a r
Brown Ronald E.
Dodwell Glenn W.
Gislason Jason J.
Morton Robert W.
Jolly Lynda S.
Langel Wayne A.
Phillips Petroleum Company
Strickland Jonas N.
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