JPH07163884A - Hydrogen treating catalyst of cracked light oil fraction - Google Patents

Abstract

PURPOSE:To produce a pref. light oil fraction having a high cetane value, a stable hue and a low pour point and low in sulfur content by hydrogenating an aromatic nucleus contained in a catalytically cracked light oil fraction to make the same naphthenic simultaneously with deep desulfurization. CONSTITUTION:A hydrogen treating catalyst of a cracked light oil fraction contains at least one kind of a metal (A) selected from group VIB metals, at least one kind of a metal (B) selected from group VIII metals and at least one kind of a metal (C) selected from Re and Ir as active metal components. The content of the component (C) is 0.1-10wt.% with respect to (A) and (B) and the amt. of all active metals supported on a carrier.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for hydrotreating catalytically cracked gas oil fraction and a method for hydrotreating cracked gas oil fraction using the same.

[0002]

2. Description of the Related Art Diesel oil used in Japan is straight-run gas oil that is fractionated from crude oil by an atmospheric distillation unit. It is hydrodesulfurized by a desulfurization unit and used as a product fuel. There is. At this time, the light oil obtained depending on the type of crude oil contains a large amount of wax and has a high pour point. In addition, the pour point rises because the boiling point range of gas oil widens due to seasonal fluctuations in product planning and fluctuations in demand trends. In this case, if necessary, a fluidity improver is added, or catalytic dewaxing is performed using a zeolite catalyst to improve fluidity. In addition, the sulfur content of the product gas oil will be required to be 0.05 ppm or less in 1997 from the viewpoint of environmental protection.

On the other hand, as an apparatus for the production of gasoline, FCC which hydrodesulfurizes a vacuum gas oil fraction obtained by vacuum distillation and uses it as a raw material for catalytic cracking, and atmospheric residual oil are applied to a direct fluid catalytic cracking apparatus. , Catalytically decomposed R
There is an FCC. In addition to gasoline from these devices,
A cracked gas oil fraction corresponding to gas oil is obtained. The cracked gas oil fraction obtained from FCC is partially mixed with straight-run gas oil in the United States and Europe and used as gas oil. The cracked gas oil fraction has a low pour point and a sulfur content of about 0.2 wt%, but has a cetane number of about 25 and very poor hue stability. Also,
The sulfur content of the fraction obtained from RFCC is very high. In Japan, cracked gas oil fractions having the above-mentioned drawbacks do not satisfy the product plan as gas oils in Japan, and are therefore mainly used as components of heavy fuel oil A.

From a compositional point of view, these cracked gas oil fractions are mainly composed of aromatic components that are stable in the reaction, so that the cetane number is low, and if the FCC reaction conditions become strict, the aromaticity increases accordingly. , And the cetane number is lower. At the same time, the hue stability becomes poor. The types of sulfur compounds contained in this fraction are mainly benzothiophenes, which are relatively poor in reactivity.

Therefore, regarding such cracked gas oil fraction, by utilizing the characteristic of having a low pour point, it is possible to improve the cetane number by finding a condition that hydrogenates an aromatic ring and converts it to naphthene and at the same time desulfurization is possible. Improved hue stability,
It becomes possible to make a low-sulfur fraction by force, and it is possible to provide a product having an excellent commercial value as this fraction as a gas oil or a component of a heavy oil A.

[0006]

[Purpose] Therefore, an object of the present invention is to obtain a high cetane number, a stable hue, and a low fluidity by nuclear hydrogenation of aromatics contained in a catalytically cracked gas oil fraction, naphthenation, and deep desulfurization at the same time. The point is to provide a hydrotreating catalyst for a cracked gas oil fraction capable of producing a preferable gas oil fraction having low sulfur, and a hydroprocessing method using the same.

[0007]

The first aspect of the present invention is that (A) at least one metal selected from the group consisting of Group 6B of the periodic table, preferably Mo and W, and (B) a group 8 metal of the periodic table. Is a catalyst containing, as an active metal component, at least one metal selected from the group consisting of Co and Ni, and at least one metal selected from the group consisting of (C) Re and Ir. ) The content of the component is (A),
(B) and the total amount of active metals supported on the carrier,
It relates to a hydrotreating catalyst of a cracked gas oil fraction of 0.1 to 10% by weight, preferably 1 to 5% by weight.

The carrier is alumina-based inorganic oxide or alumina-based inorganic oxide 98 to 50% by weight and zeolite 2 to
It is preferably a mixture with 50% by weight. As the alumina-based inorganic oxide, alumina, alumina-boria, alumina-silica, alumina-titania, alumina-zirconia, etc. can be used. The alumina used here is preferably γ-alumina.

In preparing the alumina carrier, a sulfuric acid band, sodium aluminate, and aluminum alkoxide are neutralized and hydrolyzed as an alumina starting material to obtain an alumina hydrate. This is aged or dried at 100 to 120 ° C. without aging to give a pseudo-boehmite gel. The γ-alumina carrier having a crystallite diameter d020 in the range of 45 to 60 A is obtained by molding, molding and firing at 450 to 550 ° C. In addition, in this series of operations, the pore size of the carrier is such that 25% or more of the pore size in the pore distribution is in the range of pore radius 25 to 75A, and the carrier alumina is degassed at 400 to 600 ° C. Is preferably an acidic color with an indicator such as benzeneazizophenylamine in a specific water solvent and has a Hammett acid function value H ₀ of +1.5 or less.

When the mixture of the above-mentioned alumina-based inorganic oxide and zeolite is used as a carrier, faujasite type Y-type zeolite is particularly preferable. Zeolite powder is 2 to 50 wt%, preferably 10
In the case of coexisting with ˜25 wt%, when using the alumina hydrate obtained by neutralizing and decomposing the above-mentioned alumina starting material, it is washed to remove Na ⁺ ions and SO ₄ ²⁻ ions and then hydrated. A predetermined amount of zeolite is added to the product. When alumina hydrate is used by hydrolysis, a predetermined amount of zeolite is suspended in the hydrolysis solution. Subsequent drying, raiding, molding and firing procedures are as described above. Further, this zeolite may be mixed in a predetermined amount at the stage of dried pseudo-boehmite gel.

When zeolite is used as the carrier component, it is preferable to prepare the mixture carrier described above after the component (C) is supported on the zeolite in advance.
As a specific method thereof, the amount of water absorbed by the zeolite is determined in advance, a predetermined amount of metal salt of Re or Ir is dissolved in the amount of water in charge thereof, and the metal salt solution is sprayed on the degassed zeolite in vacuum. And then absorbed. The metal-supported zeolite is dried at 120 ° C and then calcined at 450 to 600 ° C. This metal-supported zeolite is used for compounding with alumina hydrate by the method described above.

The method for supporting the active metal component on the carrier is not particularly limited, but the impregnation method is the most preferable. The amount of supported metal is 100 to 20 parts by weight of component (A), preferably 12 to 18 parts by weight, 2 to 8 parts by weight of component (B), preferably 3 to 7 parts by weight, and component (C) per 100 parts by weight of the carrier. 0.1 to 10 parts by weight, preferably 0.2
It is used in a proportion of up to 6 parts by weight. However, (A), (B)
The components are oxides, and only the component (C) is a metal. Mo is in the form of molybdate, W is in the form of ammonium tungstate, Co is in the form of cobalt nitrate, Ni is in the form of nickel nitrate, and Re In the case of (1), it is used in the form of rhenium oxide, ammonium perleate, etc., and in the case of Ir, it is used in the form of iridium chloride, and both are impregnated as an aqueous solution into a carrier, dried and calcined to obtain a catalyst.

At this time, the combination of active metals is Mo.
-Ni-Re, Mo-Co-Re, Mo-Ni-Ir,
A combination of Mo-Co-Ir, W-Ni-Re, W-Ni-Ir and the like is preferable. As a more specific example of the method for preparing the catalyst, first, a solution of Mo salt or tungstate is prepared, and first, a carrier is impregnated with a predetermined amount, dried, and then a solution of Co or Ni salt prepared. A predetermined amount is impregnated with, dried, and fired. Then Re or I
A predetermined amount of metal is supported by an aqueous solution of r salt at 120 ° C.
And dried and calcined at 350 to 500 ° C. to obtain a catalyst.

On the other hand, instead of the above-mentioned one-step firing method, a two-step firing method can be adopted. That is, first of all, Mo
Alternatively, the carrier is impregnated with a predetermined amount of metal by the W salt solution, dried and fired. Then, a predetermined amount of metal is impregnated with a Co or Ni salt solution, dried and fired. Then, a predetermined amount of metal is impregnated with an aqueous solution of Re or Ir salt, dried at 120 ° C., and then calcined at 350 to 500 ° C. to obtain a catalyst. In the second aspect of the present invention, the catalytic cracking gas oil fraction is reacted in the presence of the above catalyst at a reaction temperature of 300 to 400 ° C., preferably 320 to 370 ° C., and a reaction pressure of 30 to 150 kg /
cm ² , preferably 50 to 100 kg / cm ² , liquid space velocity 1 to 5 L / L hr ^-1 , preferably 1 to 3 L / L
It is characterized in that it is hydrotreated under the condition of hr ⁻¹ , whereby the desulfurization efficiency, the hue stability and the cetane number can be improved.

[0015]

【Example】

Example 1 A γ-alumina carrier having an average pore size of 73Å was prepared by the method disclosed in Japanese Patent Application No. 4-155583, and zeolite was mixed in the preparation process. This preparation was performed as follows. 2 liters of pure water and 1 isopropyl alcohol in a 5 liter container made of enamel
Take 1 liter of mixed solution and warm to 60 ° C. Then, 1 kg of aluminum isopropoxide powdered by a crusher in a dry box and 72 g of Y-type zeolite powder ion-exchanged with ammonium nitrate into H-type are added, and stirred vigorously for 20 minutes for hydrolysis. After hydrolysis,
Excess hydrolyzed solution is removed by filtration, vacuum dried at room temperature and then dried at 120 ° C. for 2 hours. Water was added to the obtained sample so that the water content became 60%, and extrusion molding was performed.
After drying at 20 ° C. for 2 hours, it was further calcined at 530 ° C. for 2 hours to obtain a catalyst carrier. With respect to this carrier, an ammonium molybdate aqueous solution and a nickel nitrate aqueous solution were used to carry 16.2 wt% of active metal species as molybdenum oxide and 4.1 wt% of nickel by a usual two-step impregnation method. An aqueous solution of ammonium perrhenate was used for supporting 1.0 wt% of Re by a usual impregnation method.

Using this catalyst, the reaction temperature is 350 ° C., the reaction pressure is 70 kg / cm ² , the liquid space velocity is ² L / L hr ^-1 ,
The following raw materials (Table 1) were hydrotreated under the gas ratio of 500 L / L.

[Table 1] The results are shown in Table 2. In addition, as a comparative example, the results obtained by using a catalyst prepared by the same method and not supporting Re is also shown.

[Table 2] As is clear from the above results, the catalyst of the present invention has high desulfurization activity and hydrogenation activity, and the hue and cetane index of the obtained product are improved.

Example 2 A γ-alumina carrier having an average pore size of 73Å was prepared by the method disclosed in Japanese Patent Application No. 4-155583, and zeolite was mixed in the preparation process. This preparation was performed as follows. First, 80% Y-type zeolite was prepared by using an aqueous solution of ammonium nitrate having a concentration of 1 mol.
Ion exchange with ammonium salts at ° C. Next this is 2
H-type Y zeolite is prepared by drying for 120 hours at 120 ° C. and further calcining at 540 ° C. for 3.5 hours. An aqueous solution of ammonium perrhenate was used as the carrier to add 4 wt.
% Support. Next, a mixed solution of 2 liters of pure water and 1 liter of isopropyl alcohol is placed in a 5 liter container made of enamel and heated to 60 ° C. Then, 1 kg of aluminum isopropoxide powdered by a crusher in a dry box and 114 g of Re-supported Y-type zeolite after ion exchange are added, and stirred vigorously for 20 minutes for hydrolysis. After hydrolysis, the excess hydrolysis solution is removed by filtration, vacuum dried at room temperature, and then dried at 120 ° C. for 2 hours. Water was added to the obtained sample so as to have a water content of 60%, the mixture was extruded and dried at 120 ° C. for 2 hours, and then 53
It was calcined at 0 ° C. for 2 hours to obtain a catalyst carrier. With respect to this carrier, an ammonium molybdate aqueous solution and a cobalt nitrate aqueous solution were used to carry 16.2 wt% of active metal species as molybdenum oxide and 5.1 wt% of cobalt oxide by a normal two-step impregnation method. The zeolite content of this catalyst corresponds to 15 wt%, and the Re loading amount corresponds to 0.6 wt%.

Using this catalyst, the reaction temperature is 350 ° C., the reaction pressure is 70 kg / cm ² , the liquid hourly space velocity is 3 L / L hr ^-1 ,
The raw material (see Table 1) was hydrotreated under a gas ratio of 250 L / L. The results are shown in Table 3. As a comparative example, the results obtained for the catalyst prepared by using γ-alumina as the carrier and cobalt and molybdenum as the supporting metal under the same preparation conditions except that zeolite was added are also shown.

[Table 3] As is clear from the above results, the catalyst of the present invention has high desulfurization activity and hydrogenation activity, and the hue and cetane index of the obtained product are improved.

[0019]

(Effects) (1) The catalyst of the present invention has high desulfurization activity and hydrogenation activity. (2) The gas oil fraction obtained by the catalyst of the present invention has a high cetane number, a stable hue and little coloring, and a low pour point,
It has low sulfur.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C10G 45/50 2115-4H 45/54 2115-4H (72) Inventor Osamu Yamase Kasumigaseki, Chiyoda-ku, Tokyo 3-2-5 Showa Shell Sekiyu Co., Ltd.

Claims (5)

[Claims] 1. At least one metal selected from the group consisting of metals of Group 6B of the periodic table (A) and at least one metal selected from group of Group 8 metals of the periodic table (B). , (C) at least one metal selected from the group consisting of Re and Ir as an active metal component, wherein the content of the (C) component is the (A), (B) and the carrier. 0.1 to 1 based on the total amount of active metal supported on
Hydrotreating catalyst for cracked gas oil fraction, which is 0% by weight. 2. The (A) is at least one metal selected from the group consisting of Mo and W, and the (B) is
Is at least 1 selected from the group consisting of Co and Ni
The hydrotreating catalyst for a cracked gas oil fraction according to claim 1, which is a metal of a type. 3. The carrier is alumina-based inorganic oxide or 98-50% by weight of alumina-based inorganic oxide and zeolite 2
The catalyst for hydrotreating a cracked gas oil fraction according to claim 1 or 2, which is a mixture with about 50% by weight. 4. The Hammett acidity function of the carrier is H ₀ ≦ +
The hydrotreating catalyst for a cracked gas oil fraction according to claim 1, wherein the hydrotreating catalyst is 1.5. 5. The cracked gas oil fraction is used in the presence of the catalyst according to claim 1, 2, 3 or 4, a reaction temperature of 300 to 400 ° C., a reaction pressure of 30 to 150 Kg / cm ² , and a liquid space velocity of 1 to 5 L.
/ L hr ⁻¹ , a hydrotreating method of a cracked gas oil fraction, which is characterized in that it is treated under the condition of