Mineral oils: processes and products – Chemical conversion of hydrocarbons – Plural serial stages of chemical conversion
Reexamination Certificate
1999-12-07
2003-05-27
Griffin, Walter D. (Department: 1764)
Mineral oils: processes and products
Chemical conversion of hydrocarbons
Plural serial stages of chemical conversion
C208S057000, C208S210000, C208S211000, C208S212000, C208S25100H, C208S25400R
Reexamination Certificate
active
06569314
ABSTRACT:
BACKGROUND OF THE DISCLOSURE
1. Field of the Invention
The present invention relates to a process for upgrading a liquid petroleum or chemical stream wherein said stream flows countercurrent to the flow of a treat gas, such as a hydrogen-containing gas, in at least one reaction zone. At least a fraction of up flowing vapor product is condensed to produce a condensate comprised of the heavier fraction of the vapor phase product stream and a lighter remaining vapor stream. The condensate and potentially the lighter remaining vapor stream are further hydroprocessed.
2. Background of the Invention
There is a continuing need in the petroleum refining and chemical industries for catalyst and process technology that result in increase yields of desirable products and lower yields of undesirable components, especially those related to environmental concerns. One such process technology, hydroprocessing, has been subjected to increasing demands for improved heteroatom removal, aromatic saturation, and boiling point reduction. More active catalysts and improved reaction vessel designs are needed to meet these demands. Countercurrent hydroprocessing, where the liquid feedstream flows counter to upflowing treat gas, has the potential of meeting some of these demands because they offer certain advantages over co-current process where the liquid feedstream and treat gas flow co-currently. Countercurrent hydroprocessing is well known, but it has never reached its commercial potential, primarily because of flooding problems. Within a countercurrent flow reactor the up flowing treat gas becomes saturated with reaction products and lighter components of the feed. Typical reaction products of consequence are H
2
S, NH
3
, H
2
O, and light hydrocarbon products due to cracking, saturation, or heteroatom removal. These species increase the mass flux of the vapor phase thereby reducing the hydraulic capacity of a given diameter reactor; they also depress hydrogen partial pressure thereby reducing favorable reaction kinetics and thermodynamics. The condensable portions of these species present additional problems because as they move up the reactor into cooler or reduced treat gas (due to consumption) regimes they may condense increasing the down flowing liquid rate. This phenomenon can create a reflux loop within the reactor that can exceed the fresh feed rate. The refluxing is detrimental for two reasons: hydraulic capacity of the given reactor diameter is reduced and feed dilution results in less favorable reaction kinetics and thermodynamics.
A countercurrent process is disclosed in U.S. Pat. No. 3,147,210 that teaches a two-stage process for the hydroprocessing-hydrogenation of high boiling aromatic hydrocarbons. The feedstock is first subjected to catalytic hydroprocessing, preferably in co-current flow with a hydrogen-rich treat gas, then subjected to hydrogenation over a sulfur-sensitive noble metal hydrogenation catalyst countercurrent to the flow of a hydrogen-rich gas. U.S. Pat. Nos. 3,767,562 and 3,775,291 disclose a similar process for producing jet fuels, except the jet fuel is first hydrodesulfurized prior to two-stage hydrogenation. U.S. Pat. No. 5,183,556 also discloses a two-stage concurrent-countercurrent process for hydrofining-hydrogenating aromatics in a diesel fuel stream. Any resulting vapor-phase reaction products are swept upwards by the upward-flowing treat gas. Such vapor-phase reaction products may include relatively low boiling hydrocarbons and heteroatom components, such as H
2
S and NH
3
, as well as a heavy hydrocarbon tail gas. The heavier molecules in the vapor phase product of countercurrent hydroprocessing decrease its quality and make further hydroprocessing of the vapor phase product difficult.
Therefore, there still exists a need for improved countercurrent hydroprocessing reaction designs.
SUMMARY OF THE INVENTION
In accordance with the present invention there is provided a process for hydroprocessing a hydrocarbonaceous feedstream, which process comprises:
(a) introducing said feedstream into a reaction vessel upstream from at least one reaction zone and passing said feedstream through one or more reaction zones operated at hydroprocessing conditions, wherein each reaction zone contains a bed of hydroprocessing catalyst;
(b) introducing a hydrogen-containing treat gas at the bottom of said reaction vessel and passing it upward through at least one reaction zone countercurrent to the flow of liquid feedstream, thereby reacting with said feedstream in the presence of said hydroprocessing catalysts and resulting in a liquid phase product stream and a vapor phase product stream;
(c) passing the liquid phase product out of the bottom of said reaction vessels;
(d) removing the vapor phase product stream overhead of said reaction zones;
(e) condensing a portion of said vapor phase product stream to produce a liquid stream comprised of the higher boiling point fractions and a vapor stream comprised of hydrogen-containing treat gas and the lower boiling point fractions; and
(f) passing said liquid phase stream with a hydrogen containing treat gas through a trickle bed reactor operated at hydroprocessing conditions and containing a hydroprocessing catalyst.
In a preferred embodiment of the present invention the hydrogen-containing treat gas in (f) is fresh hydrogen-containing treat gas.
In another preferred embodiment of the present invention the hydrogen-containing treat gas in (f) is the vapor stream of (e).
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Ellis Edward S.
Iaccino Larry L.
ExxonMobil Research and Engineering Company
Griffin Walter D.
Hughes Gerard J.
Singleton Wilson Erika
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