Hydroprocessing using bulk group VIII/group vib catalysts

Details Hydroprocessing using bulk group VIII/group vib catalysts Hydroprocessing using bulk group VIII/group vib catalysts

2001-07-09

2004-07-06

Griffin, Walter D. (Department: 1764)

Mineral oils: processes and products

Refining

Sulfur removal

C208S21600R, C208S108000, C208S215000, C208S25400R, C208S217000, C208S113000

Reexamination Certificate

active

06758963

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to the hydroprocessing of petroleum and chemical feedstocks using bulk Group VIII/Group VIB catalysts. Preferred catalysts include those comprised of Ni—Mo—W.
BACKGROUND OF THE INVENTION
As the supply of low sulfur, low nitrogen crudes decrease, refineries are processing crudes with greater sulfur and nitrogen contents at the same time that environmental regulations are mandating lower levels of these heteroatoms in products. Consequently, a need exists for increasingly efficient desulfurization and denitrogenation catalysts.
In one approach, a family of compounds, related to hydrotalcites, e.g., ammonium nickel molybdates, has been prepared. Whereas X-ray diffraction analysis has shown that hydrotalcites are composed of layered phases with positively charged sheets and exchangeable anions located in the galleries between the sheets, the related ammonium nickel molybdate phase has molybdate anions in interlayer galleries bonded to nickel oxyhydroxide sheets. See, for example, Levin, D., Soled, S. L., and Ying, J. Y., Crystal Structure of an Ammonium Nickel Molybdate prepared by Chemical Precipitation. Inorganic Chemistry, Vol. 35, No. 14, p. 4191-4197 (1996). The preparation of such materials also has been reported by Teichner and Astier, Appl. Catal. 72, 321-29 (1991); Ann. Chim. Fr. 12, 337-43 (1987), and C. R. Acad. Sci. 304 (II), #11, 563-6 (1987) and Mazzocchia, Solid State Ionics, 63-65 (1993) 731-35.
Now, when molybdenum is partially substituted for by tungsten, an amorphous phase is produced which upon decomposition and, preferably, sulfidation, provides enhanced hydrodenitrogenation (HDN) catalyst activity relative to the unsubstituted (Ni—Mo). phase.
SUMMARY OF THE INVENTION
In accordance with this invention there is provided a process for hydroprocessing a hydrocarbon feedstock, which process comprises contacting said feedstock, at hydroprocessing conditions, with a bulk catalyst comprised of at least one Group VIII metal and two Group VIB metals, which catalyst comprises a bulk metal catalyst containing non-noble Group VIII metal molybdate in which at least a portion but less than all of the molybdenum is replaced by tungsten. The hydroprocessing process is selected from at least one of hydrodesulfurization, hydrodenitrogenation, hydrodemetallation, hydrodearomatization, hydroisomerization, hydrodewaxing, hydrotreating, hydrofining and hydrocracking.
In a specific embodiment of the present invention, there is provided a process for preparing a lubricating oil basestock containing at least about 90% saturates which comprises:
(a) passing a feedstock to a hydrotreating zone containing at least one hydrotreating reactor containing a hydrotreating catalyst;
(b) hydrotreating the feedstock in the presence of the hydrotreating catalyst under hydrotreating conditions wherein the hydrotreating catalyst is a bulk metal catalyst comprising non-noble Group VIII metal molybdate in which at least a portion but less than all of molybdenum is replaced by tungsten to produce a hydrotreated feedstock; and
(c) fractionating the hydrotreated feedstock.
In another embodiment of the invention, there is provided a process for preparing a lubricating oil basestock containing at least about 90% saturates which comprises:
(a) passing a feedstock to a first hydrotreating zone containing at least one hydrotreating reactor containing a first non-bulk metal hydrotreating catalyst;
(b) hydrotreating the feedstock in the presence of the first hydrotreating catalyst under first hydrotreating conditions wherein the first hydrotreating catalyst comprises at least one Group VIB and at least one non-noble Group VIII metal on a refractory oxide support to produce a first hydrotreated feedstock;
(c) passing at least a portion of the first hydrotreated feedstock to a second hydrotreating zone containing at least one hydrotreating reactor containing a second hydrotreating catalyst;
(d) hydrotreating the first hydrotreated feedstock in the second hydrotreating zone under second hydrotreating conditions wherein the second hydrotreating catalyst in said second hydrotreating zone is a bulk metal catalyst comprising non-noble Group VIII metal molybdate in which at least a portion but less than all of molybdenum is replaced by tungsten to produce a second hydrotreated feedstock;
(e) fractionating the second hydrotreated feedstock.
In yet another embodiment, there is provided a process for preparing a petroleum oil containing at least about 90% saturates which comprises:
(a) passing a feedstock to a hydrotreating zone containing at least one hydrotreating reactor containing a hydrotreating catalyst;
(b) hydrotreating the feedstock in the presence of the hydrotreating catalyst under hydrotreating conditions wherein the hydrotreating catalyst is a bulk metal catalyst comprising non-noble Group VIII metal molybdate in which at least a portion but less than all of molybdenum is replaced by tungsten to produce a hydrotreated feedstock;
(c) fractionating the hydrotreated feedstock to produce a first basestock;
(d) passing the first basestock to a hydrogenation zone containing at least one hydrogenation reactor containing a hydrogenation catalyst;
(e) hydrogenating the first basestock in the presence of the hydrogenation catalyst under hydrogenation conditions wherein the hydrogenation catalyst comprises at least one Group VIII metal; and
(f) fractionating the hydrogenated product from step (e) to produce a petroleum oil containing at least about 90% saturates.
In another preferred embodiment of the present invention the catalyst composition is prepared by a process which comprises contacting the Group VIII non-noble metal component with the Group VIB metal components in the presence of a protic liquid wherein during contacting not all of the Group VIB and/or Group VIII non-noble metals are in solution.
The preferred catalyst composition of the present invention can be further described as a bulk mixed metal oxide which is preferably sulfided prior to use, and which is represented by the formula:
(X)
b
(Mo)
c
(W)
d
O
z
.
wherein X is non-noble Group VIII metal, the molar ratio of b: (c+d) is 0.5/1 to 3/1, preferably 0.75/1 to 1.5/1, more preferably 0.75/1 to 1.25/1;
The molar ratio of c:d is preferably >0.01/1, more preferably >0.1/1, still more preferably 1/10 to 10/1, still more preferably 1/3 to 3/1, most preferably substantially equimolar amounts of Mo and W, e.g., 2/3 to 3/2; and z=[2b+6(c+d)]/2.
The essentially amorphous material has a unique X-ray diffraction pattern showing crystalline peaks at d=2.53 Angstroms and d=1.70 Angstroms.
The mixed metal oxide is readily produced by the decomposition of a precursor having the formula:
(NH
4
)
a
(X)
b
(MO)
c
(W)
d
O
z
wherein the molar ratio of a:b is ≦1.0/1, preferably 0-1; and X, b, c, and d, are as defined above, and z=[a+2b+6(c+d)]/2. The precursor has similar peaks at d=2.53 and 1.70 Angstroms.
Decomposition of the precursor may be effected at elevated temperatures, e.g., temperatures of at least about 300° C., preferably about 300-450° C., in a suitable atmosphere, e.g., inerts such as nitrogen, argon, or steam, until decomposition is substantially complete, i.e., the ammonium is substantially completely driven off. Substantially complete decomposition can be readily established by thermogravimetric analysis (TGA), i.e., flattening of the weight change curve.


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George A. Olah, Hydrocarbon Chemistry, 1995, p. 30.

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