JPH0813338B2 - Residual oil hydrocracking catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a residual oil, particularly a vacuum distillation residual oil to a boiling point range of 170 to 3
The present invention relates to a hydrocracking catalyst capable of obtaining a high yield of a middle distillate of about 60 ° C. and also having good product properties of a distillate of 360 ° C. or higher.

BACKGROUND OF THE INVENTION Recent trends in petroleum include heavy crude oil produced and lighter demand. Therefore, the decomposition of heavy fractions, especially residual oil, has become an important issue.

Therefore, as one decomposition method, fluid catalytic cracking method (FCC)
Is widely practiced and has become an effective means. However, fluid catalytic cracking is suitable for producing gasoline and LPG, but it also produces a lot of coke, and the yield of kerosene and gas oil, which are generally called middle distillates, is low, and at the same time, the proportion of aromatics is high. Since it is abundant, it does not have favorable product properties. The same applies to the heavy fraction obtained.

Therefore, as a method for obtaining middle distillates, hydrocracking of vacuum gas oil has been considered and has been actually adopted. However, the use of only vacuum gas oil will increase the amount of residual oil, so the problem of this treatment cannot be solved, and the importance of establishing hydrocracking technology that can obtain an intermediate fraction from residual oil is high. .

[Problems to be Solved by Conventional Techniques and Inventions] Residual oil contains a large amount of metal components such as vanadium and nickel, and also contains large molecules such as asphaltene, which causes coke formation. The active sites on the catalyst are covered with the metal components and the generated coke, and the pores are clogged, so that the catalyst is easily deteriorated and the life is shortened.

On the other hand, in order to improve the decomposition rate, it is usual to give solid acidity to the carrier as a decomposition active point. Examples of the solid acid carrier having a decomposing activity include silica / alumina, zeolite, alumina / boria, alumina / zirconia and the like. However, according to our research, no matter what kind of solid acid carrier is used, if residual oil is used as a raw material,
It is known that the decomposition activity disappears within a short period of time and the difference in the decomposition rate between carriers disappears.

Therefore, the reaction temperature is usually set high in order to improve the decomposition rate, which improves the decomposition rate, desulfurization rate, denitrification rate, demetalization rate, and the like. However, it is known that the properties of the product obtained at that time, particularly the properties of the fraction having a boiling point of 360 ° C. or higher, deteriorate. In other words, this fraction is likely to cause sludge, which causes troubles during operation, transportation or storage. As a quantification method for sludge, toluene insoluble matter is measured.
If this is 0.05 wt% or less, preferably 0.03 wt% or less, there is no problem. When a high decomposition rate is obtained at a high temperature using an ordinary catalyst, for example, when the decomposition rate is 50 to 60%, the toluene insoluble content may be 0.1 wt%.

The product properties of the fraction are mainly determined by the toluene insoluble content, and the more the toluene insoluble content is, the less preferable the product is. Hydrocracking of heavy oil is under severe conditions (high temperature, low LH
Since SV) is required, the production rate of coke is high, and the problem of line blockage hinders long-term operation. Therefore, in order to carry out hydrocracking of heavy oil, it is necessary to develop a catalyst having a high cracking rate, a small amount of coke, and a favorable product property.

Many methods have been proposed so far for the hydrocracking of heavy oil. For example, as those utilizing a solid acid, JP-A-57-103588, JP-A-57-207546, JP-A-58-207949, JP-A-59-92026, JP-A-59-92026. -105844 gazette, etc., and many others. However, as described above, there is no effect when the residual oil is used as the raw material. Further, boron, such as adding components such as phosphorus to the carrier, or as those that control the pores of the carrier, JP 614533, JP 61-126196,
There are JP-A-62-74455 and JP-B-62-25418. It is said that the addition of boron or phosphorus is effective in improving hydrogenation activity and desulfurization activity. On the other hand, it is preferable to provide a reaction field suitable for the residual oil by controlling the pores, and at the same time, it is effective in preventing clogging and extending the life. However, there has been no one that has a preferable additive and a preferable pore structure, for example, one having a pore diameter of 100 Å or more, and no one considering the product properties to be obtained.

The present invention provides a hydrocracking catalyst for a residual oil, which has a high yield of an intermediate distillate having a boiling point range of about 170 to 360 ° C. from a residual oil and has good product properties of a distillate having a boiling point of 360 ° C. or higher. The purpose is to do.

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, control the pores of the carrier so that the average pore diameter is not less than a certain level, and boron is used as an additive. We have found a catalyst which, by adding a compound, can obtain a product having a high yield of middle distillate and good product properties of heavy distillate in hydrocracking of residual oil.

That is, according to the present invention, the alumina carrier has Ni, Co, W, Mo,
1 to 30 wt% of at least one active metal selected from V as an oxide, and 1 to 1 of a boron compound as an oxide.
The surface area of supporting 10 wt% is 150 m ² / g or more, the total pore volume is 0.4 ml / g or more, the average pore diameter is 100Å or more.
The residue hydrocracking catalyst is characterized in that the volume occupied by 100 to 200Å pores is at least 70% of the total pore volume.

The alumina carrier used in the present invention can be prepared by a known preparation method. For example, an aluminum salt such as aluminum sulfate is neutralized with an alkali such as ammonia, or an aluminate such as sodium aluminate is added, and an appropriate alkali is added to the produced alumina hydrate to form an alumina hydrate. Adjust the pH of the slurry to a weak alkaline of 8-10,
It is obtained by aging at 100 ° C. to produce pseudo-boehmite, kneading the pseudo-boehmite, molding, drying and firing. However, if the aging is insufficient, the carrier referred to in the present invention may not be obtained. Further, it can be obtained by using commercially available boehmite powder, peptizing with an acid or the like, molding, and then drying and firing.

The metal used in the present invention may include at least one selected from Ni, Co, W, Mo and V.
-Mo, Co-Mo, Ni-Co-Mo, Ni-W, Co-W, Ni-Co-
W, Ni-V, Co-V, Co-V-Mo, etc. are considered. Preferred are Co-Mo, Ni-Mo, Ni-Co-Mo, Co-
Examples thereof include W and Ni-W. Other active metals may be contained in a small amount. The amount of the active metal supported is calculated as a metal oxide based on the total weight of the catalyst, and the range of 1 to 30 wt%, preferably 5 to 20 wt% is suitable. When compounded, Co is 0.5 to 10 wt%, Ni is 0.5 to 10 wt%, and Mo is 2 to 20%.
A range of wt%, W of 2 to 20 wt% and V of 2 to 20 wt% is preferable. The method of supporting the active metal is not particularly limited, but impregnation and supporting with an aqueous solution which is usually performed is preferable.

The boron compound used in the present invention may be either an inorganic compound or an organic compound of boron, which can be converted into boron oxide when the catalyst is calcined. For example, boric acid, ammonium borate, sodium borate, sodium perborate, orthoboric acid, tetraboric acid, boron pentasulfide, boron trichloride, ammonium biborate, calcium borate, diborane, magnesium borate, methyl borate. , Butyl borate, tricyclohexyl borate and the like.

A known method is used for supporting the boron compound. For example, a method of adding a boron compound to an alumina hydrate when manufacturing alumina and molding, a method of impregnating calcined alumina by dissolving the boron compound in water, and further dissolving the boron compound in an impregnating solution containing an active metal. For example, a method of carrying them all at once can be used.

In the present invention, the addition amount of the boron compound is calculated as an oxide based on the total weight of the catalyst and is in the range of 1 to 10 wt%, preferably 2 to 8 wt%. Addition amount of boron compound is 1wt
%, There is no effect of addition, and when the addition amount of the boron compound exceeds 10 wt%, the resulting catalyst has a small pore diameter,
Moreover, not only the production of coke increases due to the increase in the amount of acid, but the boron compound is lost from the catalyst during the reaction.

Although the reason why the boron compound is preferable as an additive is not clear, it is difficult to think that the decomposition activity is improved due to the acid sites due to the formation of alumina / boria in the case of the present invention from the above reason, and the interaction between the active metal component and the boron compound. Seems to be due to.

The catalyst surface area of at least 150 meters ² / g of the present invention, preferably 150 to 250 ² / g, an average pore diameter of 100Å or more, preferably 120～300A, total pore volume of 0.4 ml / g or more, preferably 0.5 ml / g or more, and the pore distribution is such that the volume of pores with a diameter of 100 to 200Å is at least 70% of the total pore volume, preferably 75
% Or more. If the surface area of the catalyst is less than 150 m ² / g, sufficient activity cannot be obtained. If the average pore diameter is less than 100Å, the pores are likely to be clogged and the catalyst life is shortened. When the total pore volume is less than 0.4 ml / g, the amount of metal accumulated in the feed oil on the catalyst is small. If the volume of pores having a diameter of 100 to 200Å is less than 70% of the total pore volume, the reaction field required for the conversion of molecules in the residual oil is small and the activity is not effectively expressed.

The pore structure of the catalyst of the present invention is measured by a conventional nitrogen gas adsorption method, mercury porosimetry method or the like. In the present invention, a preferable pore structure is shown, and when it is deviated from this, for example, when the pore diameter is small, the catalyst life is short, and the product properties obtained are not good. When the pore diameter is too large, the activity is low and a preferable decomposition rate and desulfurization activity cannot be expected. The catalyst of the present invention can be used in a desired shape such as spherical, tablet or columnar shape. Further, the catalyst of the present invention can be used in the form of a fixed bed, a fluidized bed or a moving bed.

The catalyst of the present invention can be used alone by filling it in the reactor, but the upper stage may be filled with a demetalization catalyst as a pretreatment catalyst. The ratio is preferably 1: 3 to 1: 1.

The residual oil referred to in the present invention is an oil containing a large amount of heavy metal components such as vanadium and nickel, and also containing large molecules such as asphaltene, for example, a residual oil obtained by atmospheric distillation or vacuum distillation of crude oil, oil sand. Alternatively, a residual oil obtained by distillation of tar sand extracted crude oil under normal pressure or reduced pressure, or a mixed oil thereof may be used.
Vacuum distillation bottom oil is preferably used in the present invention.

The reaction conditions for hydrocracking using the catalyst of the present invention cover a very wide range, but generally the reaction pressure is 20 to 200 kg /
cm ² is preferably 50 to 150 kg / cm ² , the reaction temperature is 300 to 500
C., preferably 350 to 450.degree. C., LHSV is 0.1 to 2.0, preferably 0.1 to 1.0, and hydrogen / feed oil ratio is 100 to 2000 Nl / Nl.

By cracking the residual oil using the catalyst of the present invention, the cracking rate is 50 to 60% and the yield of the middle distillate is about 13 to 20%. Further, the toluene insoluble fraction of the fraction having a boiling point of 360 ° C. or higher is 0.05 wt% or less.

[Effects of the Invention] By hydrocracking a vacuum residue or the like using a catalyst having a large pore size as described above according to the present invention, large molecules in the residue can be diffused and converted inside the catalyst, At the same time, overdecomposition was suppressed, naphtha and gas generation were suppressed, and a high decomposition rate was obtained, and at the same time, a large amount of middle distillate was obtained, and at the same time, a toluene content in the high boiling fraction was small.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and the like.

Example Example 100 g of boehmite powder was dispersed in 3 distilled water, and nitric acid was added to adjust the pH to 1. Ammonia water is added to adjust the pH to 7
Neutralized with ~ 8. The obtained alumina hydrate gel was thoroughly washed with distilled water, filtered, and kneaded by heating with a kneader to obtain a kneaded product having a water content of 75%. This was extruded, dried at 110 ° C. for 3 hours, and then calcined at 550 ° C. for 3 hours to obtain 80 g of an alumina carrier.

The temperature of the alumina carrier (250 g) prepared as described above was kept in a solution prepared by dissolving 240 g of nickel nitrate, 220 g of ammonium molybdate, 250 g of citric acid and 90 g of boric acid in 1 distilled water at 40 to 50 ° C. It was impregnated for 2 hours as it was.
After that, the carrier is taken out and left to dry at room temperature all day and night,
Further, it was dried at 110 ° C. for 3 hours and calcined at 550 ° C. for 3 hours to obtain catalyst A.

Comparative Example A catalyst B was obtained in the same manner as in Example except that the same alumina carrier as in Example was used and no off-acid was added.

Evaluation Example Table 1 shows the properties of the obtained catalysts A and B. Each catalyst was filled in a microreactor having an inner diameter of 20 mmφ, and after sulfidation, it was hydrotreated with a vacuum residue having the properties shown in Table 2 under the following conditions.

Temperature: 400 ℃ LHSV: 0.2 Pressure: 115kg / cm ² · G Hydrogen / Oil: 700Nl / Nl The reaction results are summarized in Table 3. Catalyst A of the Invention
Has a higher desulfurization rate and a higher metal removal rate than the catalyst B, and a high yield of middle distillate. Further, despite the high conversion, the toluene-insoluble content of the high boiling point fraction was small, which was preferable as a product.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C10G 47/12 2115-4H (72) Inventor Akira Inoue 3 Misawa Higashimachi, Kanagawa-ku, Yokohama-shi, Kanagawa -27 (56) References JP-A-56-133035 (JP, A)

Claims (2)

[Claims] 1. An alumina carrier having 1 to 30 as an oxidation of at least one active metal selected from Ni, Co, W, Mo and V.
wt% and 1-10 wt% of a boron compound as an oxide, the surface area is 150 m ² / g or more, the total pore volume is 0.4 ml / g or more, the average pore diameter is 100 Å or more, and the diameter is 100 to 200 Å
The residual oil hydrocracking catalyst is characterized in that the volume occupied by the pores of is at least 70% of the total pore volume. 2. The hydrocracking catalyst according to claim 1, wherein the residual oil is a vacuum distillation residual oil.