Mineral oils: processes and products – Chemical conversion of hydrocarbons – Plural serial stages of chemical conversion
Reexamination Certificate
2000-04-20
2004-11-30
Johnson, Jerry D. (Department: 1764)
Mineral oils: processes and products
Chemical conversion of hydrocarbons
Plural serial stages of chemical conversion
C208S089000, C208S210000, C208S21600R, C208S217000, C208S015000, C585S014000
Reexamination Certificate
active
06824673
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a process for producing distillate boiling range streams that are low in both sulfur and aromatics. A distillate feedstock is treated in a first hydrodesulfurization stage in the presence of a hydrogen-containing treat gas and a hydrodesulfurization catalyst, thereby resulting in partial desufurization of the stream. The partially desulfurized distillate stream is then treated in a second hydrodesulfurization stage, also in the presence of a hydrogen-containing treat gas and a hydrodesulfurization catalyst. The hydrogen-containing treat gas is cascaded from a third, downstream reaction stage, which is an aromatics hydrogenation stage,
BACKGROUND OF THE INVENTION
Environmental and regulatory initiatives are requiring ever lower levels of both sulfur and aromatics in distillate fuels. For example, proposed sulfur limits for distillate fuels to be marketed in the European Union for the year 2005 is 50 wppm or less. There are also proposed limits that would require lower levels of total aromatics as well as lower levels of multi-ring aromatics found in distillate fuels and heavier hydrocarbon products. Further, the maximum allowable total aromatics level for CARB reference diesel and Swedish Class I diesel are 10 and 5 vol. %, respectively. Further, the CARB reference fuels allows no more than 1.4 vol. % polynuclear aromatics (PNAs). Consequently, much work is presently being done in the hydrotreating art because of these proposed regulations.
Hydrotreating, or in the case of sulfur removal, hydrodesulfurization, is well known in the art and typically requires treating the petroleum streams with hydrogen in the presence of a supported catalyst at hydrotreating conditions. The catalyst is usually comprised of a Group VI metal with one or more Group VIII metals as promoters on a refractory support. Hydrotreating catalysts that are particularly suitable for hydrodesulfurization, as well as hydrodenitrogenation, generally contain molybdenum or tungsten as the Group VI metal on alumina support promoted with cobalt, nickel, iron, or a combination thereof as the Group VIII metal. Cobalt promoted molybdenum on alumina catalysts are most widely used when the limiting specifications are hydrodesulfurization, while nickel promoted molybdenum on alumina catalysts are the most widely used for hydrodenitrogenation, partial aromatic saturation, as well as hydrodesulfurization.
Much work is also being done to develop more active catalysts and to improve reaction vessel designs in order to meet the demand for more effective hydroprocessing processes. Various improved hardware configurations have been suggested. One such configuration is a co-current design where feedstock flows downwardly through successive catalyst beds and treat gas, which is typically a hydrogen-containing treat gas, also flows downwardly, co-current with the feedstock. Another configuration is a countercurrent design wherein the feedstock flows downwardly through successive catalyst beds counter to upflowing treat gas, which is typically a hydrogen-containing treat-gas. The downstream catalyst beds, relative to the flow of feed, can contain high performance, but otherwise more sulfur sensitive catalysts because the upflowing treat gas carries away heteroatom components, such as H
2
S and NH
3
, that are deleterious to sulfur and nitrogen sensitive catalysts.
Other process configurations include the use of multiple reaction stages, either in a single reaction vessel, or in separate reaction vessels. More sulfur sensitive catalysts can be used in the downstream stages as the level of heteroatom components becomes successively lower. In this regard, European Patent Application 93200165.4 teaches a two-stage hydrotreating process performed in a single reaction vessel.
Two types of process schemes are commonly employed to achieve substantial hydrodesulfurization (HDS) and aromatics saturation (ASAT) of distillate fuels and both are operated at relatively high pressures. One is a single stage process using Ni/Mo or Ni/W sulfide catalysts operating at pressures in excess of 800 psig. To achieve high levels of saturation, pressures in excess of 2,000 psig are required. The other process scheme is a two stage process in which the feed is first processed over a Co/Mo, Ni/Mo or Ni/W sulfide catalyst at moderate pressure to reduce heteroatom levels while little aromatics saturation is observed. After the first stage, the product stream is stripped to remove H
2
S, NH
3
and light hydrocarbons. The first stage product is then reacted over a Group VIII metal hydrogenation catalyst at elevated pressure to achieve aromatics saturation. Such two stage processes are typically operated between 600 and 1,500 psig.
In light of the above, there is a need for improved desulfurization/aromatic saturation process for treating feedstreams so that they can meet the ever stricter environmental regulations.
SUMMARY OF THE INVENTION
In accordance with the present invention there is provided a multi-stage process for hydrodesulfurizing and hydrogenating a distillate feedstock having a sulfur content greater than about 3,000 wppm, which process comprises:
a) reacting said feedstream in a first hydrodesulfurization stage in the presence of a hydrogen-containing treat gas, said first hydrotreating stage containing one or more reaction zones, each reaction zone operated at hydrodesulfurizing conditions and in the presence of a hydrodesulfurization catalyst, thereby resulting in a liquid product stream having a sulfur content less than about 3,000 wppm;
b) passing the liquid product stream to a first separation zone wherein a vapor phase product stream and a liquid phase product stream are produced;
c) passing the liquid phase product stream to a second hydrodesulfurization stage;
d) reacting said liquid phase product stream in a second hydrodesulfurization stage in the presence of a hydrogen-containing treat gas cascaded from, or partially cascaded from, the next downstream stage herein, said second hydrodesulfurization stage containing one or more reaction zones operated at hydrodesulfurization conditions wherein each reaction zone contains a bed of hydrotreating catalyst, thereby resulting in a liquid product stream having less than about 100 wppm sulfur;
e) passing the liquid product stream from said second hydrodesulfurization stage to a second separation zone wherein a vapor phase stream and a liquid phase stream are produced;
f) collecting said vapor phase stream;
g) passing said liquid phase stream from step e) to an aromatics hydrogenation stage; and
h) reacting said liquid phase stream in said aromatics hydrogenation stage in the presence of a hydrogen-containing treat gas, said hydrogenation stage L containing one or more reaction zones operated at aromatics hydrogenation conditions wherein each reaction zone contains a bed of aromatics hydrogenation catalyst, thereby resulting in a liquid product stream having substantially reduced levels of sulfur and aromatics.
In a preferred embodiment of the present invention, the liquid phase stream, before it passes through said aromatics hydrogenation stage is contacted with a vapor to strip dissolved gases from said liquid phase.
In a preferred embodiment of the present invention the hydrogenation stage contains two or more separate temperature zones wherein at least one of said temperature zones is operated at a temperature at least 25° C. cooler than the other zone(s).
In yet another preferred embodiment of the present invention the hydrogenation stage is operated in countercurrent mode wherein treat gas flows upwardly countercurrent to downflowing feedstock.
In another preferred embodiment, the invention further comprises combining at least a portion of the liquid product stream of step (h) with at least one of (i) one or more lubricity aid, (ii) one or more viscosity modifier, (iii) one or more antioxidant, (iv) one or more cetane improver, (v) one or more dispersant, (vi) one or more cold flow improver, (vii) one or more metals deactivator, (viii)
Ellis Edward S.
Iaccino Larry L.
Jung Henry
Lewis William E.
Stuntz Gordon F.
ExxonMobil Research and Engineering Company
Hughes Gerard J.
Johnson Jerry D.
Kliebert Jeremy J.
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