Catalyst – solid sorbent – or support therefor: product or process – Solid sorbent
Reexamination Certificate
2000-03-15
2004-01-27
Nguyen, Cam N. (Department: 1754)
Catalyst, solid sorbent, or support therefor: product or process
Solid sorbent
C502S406000, C502S407000, C502S415000, C502S355000, C502S354000, C502S348000, C502S346000, C502S343000, C502S342000, C502S338000, C502S337000, C502S336000, C502S335000, C502S332000, C502S331000, C502S330000, C502S329000, C502S327000, C502S324000, C502S323000, C502S321000, C502S318000, C502S317000, C502S316000, C502S315000, C502S314000, C502S313000, C502S312000, C502S311000, C502S310000, C502S307000, C502S263000, C502S260000, C502S259000, C502S258000, C502S255000, C502S254000, C502S253000, C502S249000, C502S
Reexamination Certificate
active
06683024
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to a sorbent composition, a process of making a sorbent composition, and to a process of using a sorbent composition for the removal of sulfur from a hydrocarbon-containing fluid.
The need for cleaner burning fuels has resulted in a continuing world-wide effort to reduce sulfur levels in hydrocarbon-containing fluids such as gasoline and diesel fuels. The reduction of sulfur in such hydrocarbon-containing fluids is considered to be a means for improving air quality because of the negative impact the sulfur has on the performance of sulfur-sensitive items such as automotive catalytic converters. The presence of oxides of sulfur in automotive engine exhaust inhibits and may irreversibly poison noble metal catalysts in the converter. Emissions from an inefficient or poisoned converter contain levels of non-combusted, non-methane hydrocarbons, oxides of nitrogen, and carbon monoxide. Such emissions are catalyzed by sunlight to form ground level ozone, more commonly referred to as smog.
Most of the sulfur in a hydrocarbon-containing fluid such as gasoline comes from thermally processed gasolines. Thermally processed gasolines such as, for example, thermally cracked gasoline, visbreaker gasoline, coker gasoline and catalytically cracked gasoline (hereinafter collectively referred to as “cracked-gasoline”) contains, in part, olefins, aromatics, sulfur, and sulfur-containing compounds.
Since most gasolines, such as for example automobile gasolines, racing gasolines, aviation gasolines, boat gasolines, and the like contain a blend of, at least in part, cracked-gasoline, reduction of sulfur in cracked-gasoline will inherently serve to reduce the sulfur levels in most gasolines such as, for example, automobile gasolines, racing gasolines, aviation gasolines, boat gasolines, and the like.
The public discussion about gasoline sulfur has not centered on whether or not sulfur levels should be reduced. A consensus has emerged that lower sulfur gasoline reduces automotive emissions and improves air quality. Thus, the real debate has focused on the required level of reduction, the geographical areas in need of lower sulfur gasoline, and the time frame for implementation.
As the concern over the impact of automotive air pollution continues, it is clear that further efforts to reduce the sulfur levels in hydrocarbon-containing fluids such as gasolines, more particularly automotive gasolines, will be required. While the current automotive gasoline products contain about 330 parts per million (ppm) sulfur by weight, the U.S. Environmental Protection Agency recently issued regulations requiring the average sulfur content in gasolines to be less than 30 ppm average with an 80 ppm maximum. By 2006, the standards will effectively require every blend of gasoline sold in the United States to meet the 30 ppm level.
In addition to the need to be able to produce low sulfur content automotive fuels, there is also a need for a process which will have a minimal effect on the olefin content of such fuels so as to maintain the octane number (both research and motor octane number). Such a process would be desirable since saturation of olefins greatly affects the octane number. Such adverse effect on olefin content is generally due to the severe condition normally employed, such as during hydrodesulfurization, to remove thiophenic compounds (such as, for example, thiophenes, benzothiophenes, alkyl thiophenes, alkylbenzothiophenes, alkyl dibenzothiophenes and the like) which are some of the most difficult sulfur-containing compounds to be removed from cracked-gasoline. In addition, there is a need to avoid a system wherein the conditions are such that the aromatic content of the cracked-gasoline is also lost through saturation. Thus, there is a need for a process wherein desulfurization is achieved and the octane number is maintained.
In addition to the need for removal of sulfur from hydrocarbon-containing fluids such as cracked-gasoline, there is also presented to the petroleum industry a need to reduce the sulfur content in other hydrocarbon-containing fluids such as diesel fuel including light cycle oils. In removing sulfur from diesel fuel by 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 of desulfurization without a significant consumption of hydrogen so as to provide a more economical process for the treatment of hydrocarbon-containing fluids such as cracked gasoline and diesel fuel including light cycle oils.
As a result of the lack of success in providing a successful and economically feasible process for the reduction of sulfur levels in hydrocarbon-containing fluids such as cracked-gasoline and diesel fuel including light cycle oils, it is apparent that there is still a need for a better process for the desulfurization of such hydrocarbon-containing fluids which has minimal effect on octane levels while achieving high levels of sulfur removal.
Further, prior art processes to produce compositions containing promoter components generally involve adding the promoter components by spray impregnation techniques which utilize an aqueous or non-aqueous solvent such as water. Such spray impregnation techniques are costly and time-consuming. Consequently, a process to produce a sorbent composition which involves adding a promoter component(s) without utilizing a spray impregnation technique or substantial quantities of an aqueous or non-aqueous solvent such as water would be of significant contribution to the art and to the economy.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a sorbent composition that can be used for the removal of sulfur from a hydrocarbon-containing fluid such as cracked-gasoline or diesel fuel including light cycle oils.
Another object of the present invention is to provide a sorbent composition comprising a promoter component selected from the group consisting of metals, metal oxides, and the like and combinations thereof distributed as a “skin” on the sorbent composition.
Yet another object of the present invention is to provide a sorbent composition having a reduced amount of metal or metal oxide components exhibiting a high reactivity to remove sulfur from hydrocarbon-containing fluids compared to a sorbent composition having a greater amount of such metal or metal oxide components.
Still another object of the present invention is to provide a method of making a novel sorbent composition which is useful in the desulfurization of a hydrocarbon-containing fluid such as cracked-gasoline or diesel fuel including light cycle oils.
Still yet another object of the present invention is to provide a method of making a novel sorbent composition which is useful in the desulfurization of a hydrocarbon-containing fluid, such as cracked-gasoline or diesel fuel including light cycle oils, which does not involve a spray impregnation technique, such as a spray impregnation technique which utilizes an aqueous or non-aqueous solvent such as water, when adding a promoter component(s) to such composition(s).
A further object of the present invention is to employ such novel sorbent composition(s) and a process(es) for the removal of sulfur, such as that found in sulfur-containing compounds, from a hydrocarbon-containing fluid, such as cracked-gasoline or diesel fuel including light cycle oils, which minimizes the consumption of hydrogen and minimizes the saturation of olefins and aromatics contained in such hydrocarbon-containing fluid.
A still further object of the present invention is to provide a desulfurized cracked-gasoline that contains less than about 100 parts per million of sulfur based on the weight of the desulfurized cracked-gasoline and which contains essentially the same amount of olefins and aromatics as are in the cracked-gasoline from which such desulfurized cracked-gasoline was made.
The present invention is based upon our discovery that
Engelbert Donald R.
Khare Gyanesh P.
ConocoPhillips Company
Jolly Lynda S.
Nguyen Cam N.
Welvaert Bronwyn A.
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