Hydrogenation catalyst and method of hydrogenating heavy oil

Details Hydrogenation catalyst and method of hydrogenating heavy oil Hydrogenation catalyst and method of hydrogenating heavy oil

2000-03-01

2002-06-04

Preisch, Nadine (Department: 1764)

Mineral oils: processes and products

Refining

Sulfur removal

C208S217000, C208S2160PP, C208S253000, C208S25100H, C208S143000, C208S144000, C208S145000, C502S313000, C502S314000, C502S315000, C502S312000, C502S332000, C502S335000, C502S337000, C502S354000

Reexamination Certificate

active

06398950

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a catalyst for hydrogenation treatment in which Mo—Ni, Mo—Co or the like is supported on an alumina-type carrier, and a method for hydrogenation treatment of heavy oil using the same. More specifically, it relates to the above-described catalyst showing a specific X-ray diffraction pattern, and a method for hydrogenation treatment of heavy oil using the same.
BACKGROUND OF THE INVENTION
In the petroleum refining, there are a large number of steps of refining various fractions through hydrogenation treatment, and a wide variety of catalysts therefor have been developed. Typical examples are a catalyst for desulfurization and denitrification of naphtha, kerosene, light oil and the like, a catalyst for desulfurization and denitrification of heavy-duty light oil, a cracking catalyst, a catalyst for desulfurization and denitrification of residual oil and heavy oil, and so forth. Of these, a catalyst which is used in a hydrogenation treatment step of treating naphtha, kerosene and light oil, which has a relatively low boiling point and which has almost no contents of metal impurities such as vanadium and the like is degraded to a small extent by the use.
Further, these catalysts were not degraded with vanadium or the like by the use, and they were degraded mostly by accumulation of a small amount of a carbonaceous material. When this was removed through burning or the like, they could be reused. Further, with respect to the removal of the carbonaceous material, since the amount of the carbonaceous material on the catalyst is small, a reusable catalyst is obtained without the need of strict burning control. Further, catalysts once used include catalysts which are degraded to a small extent, and such catalysts can be reused as they are. These catalysts are reused in the treatment of naphtha, kerosene, light oil and the like without special care.
Moreover, a catalyst for hydrogenation treatment of heavy-duty light oil and reduced pressure light oil has recently been reused through regeneration or the like. The regeneration and use methods have been also established. For example, it has been known that in a heavy-duty light oil hydrogenolysis process, a hydrogenolysis catalyst and a hydrodenitrification catalyst for its pretreatment can be regenerated and used through hydrogen activation or oxygen activation.
Regarding the catalysts used in hydrogenation treatment of these distillation oils, since stock oils treated contain less metal impurities, metals derived from raw materials, such as vanadium and the like are less accumulated on the catalysts. Further, a carbonaceous material is not only less accumulated, but also easy to burn. In the regeneration through burning, the catalyst surface does not have quite a high temperature, and a pore structure of a catalyst carrier, a supported condition and the like of an active metal phase are less changed. Thus, the catalysts could have been reused in the treatment of distillation oils such as heavy-duty light oil, reduced pressure light oil and the like (Studies in Surface and Catalysis, vol. 88 p. 199 (1994)).
However, in the hydrogenation treatment of heavy oil having a high boiling point or containing a fraction incapable of distillation, such as residual oil, metal impurities contained in stock oil and ingredients liable to carbonization, such as asphaltene and the like are present in large amounts, and large amounts of metals and carbonaceous materials are consequently accumulated on spent catalysts. Further, qualitatively, with respect to the spent catalysts on which the metals and the carbonaceous materials have been accumulated simultaneously, the carbonaceous materials cannot easily be removed through burning. Even though they are removed through burning, the pore structure of the catalyst carrier, the supported condition of the active metal phase and the like are greatly changed. Thus, a performance as a catalyst has not been expected (Catal. Today, vol. 17, No. 4, p. 539 (1993), Catal. Rev. Sci. Eng. 33 (3 & 4) p. 281 (1991)). For this reason, these spent catalysts to which vanadium is adhered to some extent have been discarded without being reused.
The present invention aims to provide a catalyst which can be utilized through regeneration treatment or the like of a catalyst not used because of deactivation by the use in a hydrogenation treatment process, and a method for hydrogenation treatment of heavy oil using the same.
DISCLOSURE OF THE INVENTION
The present inventors have assiduously conducted investigations, and have consequently found that a preferable catalyst for hydrogenation treatment can be provided by regenerating a catalyst deactivated by the use in a heavy oil hydrogenation treatment process and analyzing a crystal condition of a support metal and the like from the X-ray diffraction pattern thereof. On the basis of this finding, they have completed the present invention.
That is, the gist of the present invention is described below.
(1) A catalyst to be fed to a heavy oil hydrogenation treatment apparatus in which an inorganic oxide carrier containing alumina contains Mo, Ni and V or Mo, Co and V, a peak height ratio I
1
/I
0
according to the X-ray diffraction measurement is between 0.1 and 1.0, and I
2
/I
1
is 1.0 or less in which I
0
, I
1
and I
2
are peak heights appearing when d values of the X-ray diffraction pattern are 1.98±0.05 Å, 3.32±0.05 Å and 3.79±0.05 Å, respectively.
(2) The catalyst as recited in (1), wherein a peak height ratio I
3
/I
1
according to the X-ray diffraction measurement is 1.0 or less in which I
3
is a peak height appearing when a d value of the X-ray diffraction pattern is 3.55±0.05 Å.
(3) The catalyst as recited in (1) or (2), wherein the vanadium content is between 0.1 and 35% by weight.
(4) The catalyst as recited in any of (1) to (3), wherein the carbon content is between 0.3 and 15% by weight.
(5) The catalyst as recited in any of (1) to (4), wherein a specific surface area is between 60 and 220 m
2
/g.
(6) The catalyst as recited in any of (1) to (5), wherein a pore volume is between 0.3 and 1.2 cc/g.
(7) The catalyst as recited in any of (1) to (6), wherein the form of the catalyst is substantially cylindrical, the axial average length is between 1.6 and 10.0 mm, a product of 1.5 mm or less is 10% by weight or less, and a product of 1.0 mm or less is 5% by weight or less.
(8) The catalyst as recited in any of (1) to (6), wherein the average length of the catalyst is between 2.0 and 10.0 mm, the product of 1.5 mm or less is 10% by weight or less and the product of 1.0 mm or less is 5% by weight or less.
(9) The catalyst as recited in any of (1) to (8) which is obtained by using a catalyst in which Mo and Ni or Mo and Co are supported on an inorganic oxide carrier containing alumina in hydrogenation treatment of heavy oil, and then regenerating the catalyst through oxidation.
(10) The catalyst as recited in any of (1) to (9), wherein the molybdenum content is in the range of 0.1 to 25% by weight, and the nickel or cobalt content is in the range of 0.1 to 10% by weight.
(11) The catalyst as recited in (10), wherein the inorganic oxide carrier containing alumina contains 0.1 to 10% by weight of phosphorus.
(12) A method for hydrogenation treatment of heavy oil using the catalyst as recited in any of (1) to (11).
(13) The method as recited in (12), wherein the hydrogenation treatment is hydrodesulfurization treatment or hydrodemetallization treatment.
BEST MODE FOR CARRYING OUT THE INVENTION
The mode for carrying out the present invention is described below.
In the present invention, a catalyst which is once used in the hydrogenation treatment process of heavy oil and the like and degraded is subjected to regeneration treatments such as screening, cleaning, oxidation and the like for providing specific properties and composition, so that it can be reused as a catalyst for hydrogenation treatment.
In the heavy oil hydrogenation treatment process, the treatment of heavy oil is cond

Affiliated with

Also associated with

Rating

Hydrogenation catalyst and method of hydrogenating heavy oil does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Hydrogenation catalyst and method of hydrogenating heavy oil, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Hydrogenation catalyst and method of hydrogenating heavy oil will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2960466