JPS6274455A - Hydrodesulfurizing and hydrocracking catalyst - Google Patents

Abstract

PURPOSE:To enhance hydrodesulfurizing and hydrocracking activity, by supporting a metal of the VIb group of the Periodic Table, a ferrous metal of the Group VIII and a platinum group metal by a carrier comprising alumina or the like and specifying the specific surface area and pore volume, etc., of said carrier. CONSTITUTION:A metal of the Group VIb of the Periodic Table,a ferrous metal of the Group VIII and a platinum group metal are supported by a carrier comprising a mixture consisting of alumina, amorphous silica/alumina and Y-type zeolite to form a hydrodesulfurizing/hydrocracking catalyst. This catalyst has a specific surface area of 300-500m<2>/g and pore distribution such that the volume of pores with a pore radius of 20-300Angstrom is 0.35ml/g or more and there are one clear peaks respectively at a pore radius of 20-40Angstrom and a pore radius of 50-100Angstrom . Further, the volume of pores with a pore radius of 20-45Angstrom is 15-40% of that of pores with a pore radius of 20-300Angstrom .

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a heavy metal carrier comprising a mixture of alumina, amorphous silica/alumina, and Y-type zeolite, carrying metals of group VIb and group II of the periodic table. The present invention relates to a catalyst having excellent activity for hydrodesulfurization and hydrocracking treatment of oil.

[Problems to be solved by conventional technology and invention]

While crude oil is becoming heavier worldwide, demand for petroleum products is increasingly becoming lighter and medium-sized.

For this reason, the cracking process that converts heavy oil into high-value light oil is becoming increasingly important. The petroleum refinery industry is taking various measures to deal with this, and one of them is converting existing hydrodesulfurization equipment to cracking equipment. That is, this is a method in which hydrodesulfurization is carried out and hydrocracking is also carried out at the same time to produce medium and light components in high yield.

Hydrodesulfurization catalysts for so-called heavy oils such as atmospheric residual oil, vacuum gas oil, vacuum residual oil, etc. are catalysts in which group II metals of the periodic table, such as molybdenum, and metals of group II, such as cobalt and nickel, are supported on an alumina carrier. This type of catalyst shows high desulfurization activity and is suitable as a hydrodesulfurization catalyst, but its cracking activity is low, so high reaction temperatures or high reaction temperatures are required to obtain medium and light components in high yield. Requires harsh reaction conditions such as low liquid hourly space velocity. On the other hand, many hydrocracking catalysts have been proposed so far. In other words, silica and alumina have high acidity.

Silica/Magnesia, Alumina/Titania, Alumina/
■B group metal and 1 on solid acidic carrier such as boria
Attempts have been made to improve the resolution using catalysts supported on group metals. Catalysts using these highly acidic carriers have better cracking activity to some extent than catalysts using alumina carriers, but they still cannot exhibit sufficient cracking activity and have low desulfurization activity.

Furthermore, in recent years, hydrocracking catalysts containing zeolite have been developed for the purpose of improving the hydrocracking activity of the above-mentioned types of catalysts.

This zeolite-containing catalyst exhibits higher cracking activity than catalysts that do not contain zeolite, and has the ability to hydrocrack heavy oil under relatively mild reaction conditions. It has the disadvantage of poor selectivity and the majority of the product is naphtha and gas.

[Means for solving problems]

In order to improve the problems of conventional catalysts as described above, the present inventors have conducted various studies, and as a result, we have found that a catalyst with high efficiency is effective for both hydrodesulfurization of heavy oil and hydrocracking to produce middle distillates in high yields. As active catalysts, alumina, amorphous silica/alumina, and specific surface 1) <3o o-s o orrL'/
The present invention was achieved by discovering a catalyst having a specific pore distribution.

The non-invention will be explained in detail below.

The hydrodesulfurization/hydrocracking catalyst of the present invention includes alumina, amorphous silica, alumina, and Y-type zeola, and at least one metal of the group ■B group and at least one metal of the iron group of group ■ metals in the alumina of the support. specific surface area JOO-30θm''
/y- catalyst, ■ The volume of pores with radius -〇~3ooX is θ, 3j-71
That's all, ■ Radius -tIo X and radius! θ~io.

In addition, each shows a pore distribution with one clear peak, and ■ the volume of the pore with radius 0 -a s is the radius 03
It is in the range of 15 to qo% of the pore volume of ooX, and the radius is 95 to /! It is characterized in that the volume of the pores of ON is in the range of ss to ts of the volume of pores of radius oP-JooX.

In the present invention, "pore distribution with a clear peak" refers to a pore distribution curve in which the value obtained by differentiating the cumulative pore volume with respect to the pore radius is plotted against the radius, and the so-called pore distribution curve has a clear maximum value. It means to have. A pore distribution having one distinct peak in each specific co-region is known as a blmodal pore distribution (see, for example, Catalyst, Vol. 27). (See No. 5, pages J/& to Jug).

In the hydrodesulfurization/hydrocracking catalyst of the present invention, the carrier is composed of a mixture of alumina, amorphous silica/alumina, and Y and L zeolites, and the alumina substantially carries the desulfurization activity, and the amorphous silica・Alumina and Y-type zeolite are responsible for the decomposition activity in a pneumatic manner.

Generally, in the carrier of the catalyst, the alumina compounding needle is 3.
It is used in the range of 0 to 6θwt%, preferably 0 to 50wt%, and the blending amount of amorphous silica/alumina and Y
The blending amount of the type zeolite is -〇z (10 wt%), and the amount of amorphous silica/alumina and Y
The total blending amount of the zeolite type is used in the range of qo to 70 wtl, preferably SO to &0.0 wtl. If the amount of alumina blended is too small, the desired desulfurization activity of alumina will not be fully exhibited, whereas if it is too large.

The alumina used in the present invention has a specific surface area of ljθ~,
700 rrl / 9- indicates radius Yu~73000
The total pore volume is o, b to t, oml/P,
and the volume of the pores with radius xi s −t s o X is at least gs% of the total pore volume, and the radius
The pore volume of sX is to% or less of the total pore volume,
radius! It is desirable that the pore distribution has a clear peak at 0%10OX, and that the pore volumes with a radius of 5θ to 1OOX are o, r-o, zarnt/9-. Alumina that satisfies this condition can be produced using a known pore control method, for example, by adding water, an inorganic acid or an organic acid, and a basic nitrogen compound to boehmite produced by hydrolysis of aluminum alkoxide. After uniformly mixing and kneading and molding into the desired shape and dimensions, drying
It can be produced by firing at a temperature of ~t, ooc.

In the present invention, in order to improve the water volumization decomposition activity of the catalyst, amorphous silica/alumina as a relatively mild solid acidic substance and YfM zeolite having strong solid acidity are mixed with the above-mentioned nine alumina to form a catalyst carrier.

Amorphous silica-alumina generally has relatively high acidity and high surface area, QO-90w*% silica and/or
Consists of Q~60 wtl alumina. More specifically, the amorphous silica-alumina of the present invention has a specific surface area of 3s
o-Aso, 172, and the volume of all pores with a radius of 0 to qsoooX is 0.11-0. g d/Ii', and the volume of pores with a radius of 0 to p, tX is gs% or more with respect to the volume of all pores with a radius of 20 to tsoooX.
It is desirable that the volume of pores with radius aS to tsoX be 10% or less.

In the above-mentioned amorphous silica/alumina, relatively large molecules to be hydrogenated can enter the pores, but macromolecules such as asphaltene cannot enter the pores, so carbonaceous materials due to the decomposition of macromolecules generation and the accumulation of heavy metals and nitrogen compounds, resulting in high decomposition activity and a high middle distillate yield. If the pore radius of this amorphous silica/alumina is made smaller than the limit, it becomes difficult for molecules to be hydrogenolyzed to diffuse into the pores.
This is undesirable because the decomposition reaction is suppressed, the decomposition activity is reduced, and in addition, over-decomposition occurs due to slow molecular diffusion within the pores, and the yield of the middle distillate is also reduced. Amorphous silica-alumina satisfying the above conditions can be prepared by conventional methods similar to those known to those skilled in the art for producing synthetic silica-alumina decomposition catalysts. For example, water glass is mixed with sulfuric acid to make a silica hydrogel, then aluminum sulfate and ammonia are added to deposit alumina on the silica hydrogel. After filtering and cleaning this alumina hydrogel, it is molded into the desired shape and dimensions, dried,
By firing, amorphous silica/alumina that satisfies the above conditions can be obtained. Furthermore, commercially available silica/alumina decomposition catalysts can also be used in the amorphous silica/alumina of the present invention as long as they satisfy the above conditions. These commercially available silica
Alumina decomposition catalysts are usually available as fine particles or molded bodies. Although the fine particles can be used as they are as the amorphous silica/alumina support of the present invention,
For relatively large fine particles and molded bodies, the particle size of the particles is reduced by pulverization using a wet ball mill, dry impact mill, colloid mill, etc., and using a small particle size results in a carrier with superior mechanical strength and wear resistance. is obtained, which is preferable.

In the present invention, the above-mentioned amorphous silica and alumina, which are relatively mild solid acids, are responsible for part of the decomposition activity, and at the same time, Y-type zeolite, which has stronger solid acid properties, is also responsible for the decomposition activity. .

By using this amorphous silica/alumina and Y-type zeolite in combination, for example, compared to a catalyst in which only zeolite has decomposition activity, the amount of gaseous components by-produced is small, and the selectivity for middle distillates is high. Moreover, high resolution results can be obtained.

The Y-type zeolite used in the invention is typified by Onion Carbide's SK-'70, and can be produced by a known method. For example, "chemistry and industry", ko1%lko4i
-Co (196g) describes a method for producing Y-type zeolite. This Y-type zeolite can be used as it is as a carrier component in the present invention, but more preferably,
All of the exchangeable alkali metal ions of the Y-type zeolite are exchanged with ammonium and/or rare earth metal ions such as lanthanum and cerium by a normal ion exchange method to reduce the alkali metal ion content of the Y-type zeolite. It is desirable to use it by reducing it to below wt%. Furthermore, the Y-type zeolite of the present invention is ultra-stable Y-type zeolite.
type zeolite can also be employed. Ultra-stable Y-type zeolite is ammonium-exchanged Y-type zeolite, for example g
A method of stabilizing by dealumination using DTA etc.
It can be produced by a method of stabilizing by steaming, a method of stabilizing by repeating high-temperature firing and ion exchange, a method of stabilizing by treating with mineral powder, etc.

The ultra-stable Y-type zeolite thus obtained can be used as it is as a carrier in the present invention.

Furthermore, it can also be used as an ultra-stable Y-type zeolite that has been ion-exchanged with rare earth metal ions such as lanthanum and cerium.

The catalyst carrier of the present invention is prepared by mixing the above-mentioned alumina, amorphous silica/alumina, and Y-type zeolite in a predetermined ratio,
Molded into desired shape such as spherical, cylindrical, tablet, etc.
After drying, it is manufactured by firing at a temperature of SOO to 6θO<0>C for /-/Q hours. The support thus obtained has a high specific surface area and a pore distribution ranging from -0 to 3ooX, with a large amount of amorphous silica-alumina pores and ys-is.

XK has a large amount of alumina pores.

The specific surface area and pore distribution of the catalyst of the present invention are generally within the ranges described above for alumina and amorphous silica/alumina, which are generally used as catalyst carriers. Once selected, these can be mixed with Y-type zeolite in the usual manner, molded,
Obtained by firing.

However, the pore characteristics of these alumina and silica/alumina raw materials are not always completely sufficient conditions for the pore characteristics of the product catalyst, so ultimately, the pore characteristics of the prepared catalyst must be determined each time. It is desirable to check and make a selection. Of course, it is not at all impossible that the catalyst of the present invention may be prepared from materials whose characteristics are outside the above-mentioned range by making some modifications, so in any case, the obtained catalyst does not meet the requirements of the present invention. Then, the alumina to use,
The pore characteristics of amorphous silica/alumina are preferably within the ranges described above, but are not necessarily limited thereto.

It is supported in the form of a mixed compound of alumina and amorphous silica/alumina. More preferably, the alumina of the support includes l/lb group metals such as molybdenum and (
or) tungsten, and group VIIl metals selected from iron group metals, such as nickel and/or
Cobalt is supported on the amorphous silica/alumina carrier, and at least one metal selected from platinum group metals such as platinum, rhodium, iridium, and palladium is supported on the amorphous silica/alumina carrier. The amorphous silica of the carrier
In the present invention, it is desirable to avoid supporting alumina and Y-type zeolite with iron group metals such as group (I) group metals and group (I) metals, as this lowers the 1 decomposition activity. This is ■
This is because supporting iron group metals such as group B metals and group II metals blocks the pores of amorphous silica/alumina, lowers the surface area, and reduces acidic points, and destroys the crystal structure of Y-type zeolite. This is because it reduces the surface area and further reduces the number of acidic points. Usually, the amount of the active ingredient supported on the alumina of the carrier is
t%, and the platinum group metal of the group Ⅰ metal supported on the amorphous silica/alumina of the support also accounts for 0.0% of the final catalyst composition as a metal. OS = /wt%.

The active components of these catalysts are alumina, amorphous silica,
Before the step of mixing alumina and Y-type zeolite, alumina and amorphous silica/alumina are separately impregnated and supported with an aqueous solution containing the above components, then mixed, molded,
Drying and firing method: Amorphous silica/alumina is impregnated in advance with an aqueous solution containing the above active ingredient, dried and fired, then mixed with alumina and Y-type zeolite, molded, dried and fired. By carefully applying an aqueous solution containing the above-mentioned active ingredient to an intermediate catalyst composition consisting of alumina, Y-type zeolite, and platinum group metal-supported amorphous silica/alumina, it is selectively applied only to the alumina pores of the carrier. Any of the methods of impregnating iron group metals such as group metals and iron group metals and supporting them by drying and firing can be employed. Calcination of catalysts impregnated with active ingredients.

The process is carried out under the same conditions as in the case of producing a mixture carrier of alumina, amorphous silica/alumina and Y-type zeolite.

〔effect〕

The thus molded catalyst of the present invention exhibits excellent desulfurization and cracking activity in the hydrodesulfurization/hydrocracking treatment pressure of heavy oil, and is particularly capable of obtaining middle distillates in high yields. Hydrodesulfurization and hydrocracking treatment of heavy oil using the catalyst of the present invention can be carried out using known methods and conditions. For example, under a hydrogen pressure of 50-co00k (17 dlG), heavy oil with liquid hourly space velocity of oi-yuh-1, hydrogenated heavy oil 300-co00
By circulating the oil at 0 Httloil t, heavy oil can be effectively hydrodesulfurized and hydrocracked, and the yield of the middle distillate is high.

〔Example〕

The present invention will be explained in more detail below using Examples.

The pore distribution and volume in Examples were measured using a mercury intrusion porosimeter. The machine used is an automatic porosimeter Auto Bore Tacho 00 manufactured by Shimadzu Corporation, and the maximum pressure Hiroko θ (7k
p/c, r/l cage.

Therefore, the measurement range of pores is radius/7. g A to qso
oo X. The specific surface area was determined by the nitrogen adsorption method as pBp, r.
Calculated using the method. The machine used was Nooptomatic/Jfθ0 manufactured by Carlo Erba.

Example (1) Production of alumina carrier precursor kneaded product and alumina carrier Boehmite powder Pural SB (AI,
O, content 75%) 50? Transfer to a batch kneader and add 4<, J% nitric acid aqueous solution/Hiroshi 7? was added while kneading over about 5 minutes, and mixing was continued for an additional 25 minutes. Next, add Yu/thiammonia water 69S to the mixture. was added and stirred for 25 minutes to obtain a kneaded product (X).

This kneaded material (X) was molded using a screw set extruder with a diameter of /,
After extrusion molding to 5 m + 1, the molded product was heated at 1-0°C for 3 hours, the temperature was gradually raised in an electric furnace under dry air flow, and finally it was fired at a temperature of 5 soc for 3 hours to obtain alumina. . The obtained alumina has a specific surface area/g 7 y//
f, and the volume of all pores with a radius of 20 to 7 sooo7y is 0.7,? / d/ fP and radius ttts ~
is.

Also, the volume of the pore is g of the total pore volume? , A %, and the volume of pores with radius o -as X is 6.9% of the total pore volume, showing a pore distribution with a sharp peak at radius 67H. The pore volume of ~too'j was o, strml/f.

(2) Production of catalyst Amorphous silica/alumina molded carrier manufactured by Catalysts & Chemicals Co., Ltd. (composition: 50% Sto, SO% AI, O, specific surface area I
IJ&rrl/l, the total pore volume with a radius of 20-73;000 is 0. ! red/n), the volume of the pore with radius -〇~dasg is 0. 'I 4. What is the volume of the pores with a radius of 0 to ttsX relative to the total pore volume? /, 0%
, and the volume of a pore with radius tis~troX is! , Hirochi, and exhibits a pore distribution with a sharp peak at radius J7
After drying for 3 hours at 0C, the temperature is further raised in an electric furnace under dry air circulation, and finally SSO is applied.
It was fired at ℃ for 3 hours to support +7.5 wt % of palladium metal on the basis of the carrier. 5 oop of this palladium-supported amorphous silica/alumina carrier was transferred to a shaking ball mill (content: y s t ), and water was mixed with 15θ0? was added and pulverized between rollers to obtain a palladium-supported amorphous alumina finely pulverized product (Y).

2゜On the other hand, Y-type zeolite SK-' manufactured by lNion Carbide Co., Ltd.
l0jrθθ? was added to a 3N aqueous ammonium chloride solution, stirred at 00°C for 3 hours, and then dehydrated and washed q times.
to obtain an ammonium-exchanged Y-type zeolite (Na-containing tO, OJ wt%). Next, this ammonium-exchanged Y-type zeolite was immersed in an aqueous solution of cerium acetate (dissolved with a small amount of salt dispersion), ion-exchanged with approximately 2.2 mg of cerium ions per IY-type zeolite, dehydrated, and washed. After drying at 1-0C, cerium-exchanged Y-type zeolite (Z) was obtained.

This cerium-exchanged Y-type zeolide (cerium-exchanged Y-type zeolite content: 7 g, 9 wt%) 4.7. Fp and the above kneaded product (X), tyuj? and finely ground material (Y) i
Ko0.6? were charged into a kneader and mixed and crossed for a period of time. Next, it is molded into a cylindrical shape with a diameter of 120 cm.
After drying for 3 hours at a temperature of
wt%, palladium-supported amorphous silica/alumina content i, 70 wt%, alumina content 'I j wt
A catalyst carrier was obtained.

This Baladichum-supported carrier is g/? was first impregnated with a quinoline solution of 1.41.09-, and then the quinoline in the alumina pores of the carrier was gradually evaporated at a temperature of 7θC, and dried to a quinoline impregnation amount of 4"1.4 wt%. An aqueous solution containing 6.6 jp of ammonium molybdate and 15' lIf of nickel mesnitrate was impregnated into a quinolium-impregnated carrier, dried while gradually increasing the temperature to JooC, and then calcined at 5 soc for 3 hours to form a catalyst. / was manufactured.

Table 1 shows the amount of catalyst components supported and physical properties of Catalyst-1.

(3) Catalyst - Production of cerium-exchanged Y-type zeolite was replaced with ultra-stable Y-type zeolite (manufactured by Toyo Soda Kogyo Co., Ltd.) T8Z-3! Yu (ultra stable Y-type zeolite content 9 da, 6%, sodium content mini 0. Yu 6 wt%) 6 Yu, 71 and finely ground product (Y)-
Ultra-stable catalyst carrier composition using g co, J f, gLY type zeolite content = 7 wt%, palladium supported amorphous silica/alumina content 3 wt%, alumina content U
/ Vt% binding and quinoline containing ill 'I
Co, r wt% ammonium molybdate 7.7
? Catalyst-1 was produced by producing a catalyst carrier and supporting an active component in the same manner as in the production of Catalyst-7, except that an aqueous solution containing 2 and nickel nitrates r and l3f was used here and there.

Table 7 shows the amount of catalyst components supported and the physical properties of Catalyst-1.

(4) Production of catalyst-3 Aqueous solution II containing ammonium molybdate 7t, 49f and nickel nitrate l-,//i r,grd
The catalyst carrier was produced and the catalyst components were supported in the same manner as in the production of the catalyst, except that a catalyst was used.
3 was manufactured.

Table 7 shows the catalyst component support i> and physical properties of Catalyst-3.

(5) Production of Catalyst-Hiroshi The kneaded product (X) 92f obtained in Example (1) was charged into a kneader, and an aqueous solution containing 3 g, 96z of ammonium molybdate and 7 f of nickel nitrate J/ was prepared. , f4
- was added while kneading over 5 minutes, and further mixed and kneaded while heating and concentrating for 210 minutes. Next, the finely ground product (Y) 2 lI/ obtained in the production of catalyst-7 was added to this mixture.
%, ultra-stable Y-type zeolite of the same brand as that used in the production of Catalyst-C) 6.71%, and water SO. Thereafter, extrusion molding, drying and calcination were carried out in the same manner as in the production of catalyst-1, and ultra-stable Y-type zeolite-containing ii, 7
0 wt%, amorphous silica/alumina content fJ Ow
t%, alumina-containing liquid! (A catalyst composition consisting of 7 wt% of carrier was produced.

Table 7 shows the amount of catalyst components supported and physical properties of catalyst-q.

(6) Production of catalyst = 5 Amorphous silica/alumina molded carrier manufactured by Catalysts & Chemicals Co., Ltd. (composition: 72:810.0g% AI!O,.

Specific surface mt! l'1m'IP, the volume of all pores with a radius of 20 to 7,000 is 0. & / 艷 / n and the radius is o
-tt s The pore of X has a volume θ, j gme/f,
The volume of the pores of medium diameter θ to djX relative to the total pore volume is g
The volume of the pore with radius US~1soX is 7
．． 6 polyester, showing a pore distribution with a clear peak in the radius core
Aqueous solution of tetraamine palladium chloride containing /ml
tr,? - impregnated with. Hereinafter, υpalladium-supported amorphous silica
900f of finely pulverized alumina was obtained. This palladium-supported amorphous silica/alumina finely ground cog θ1 is put into a kneader.
The kneaded product (X) obtained in Example (1)
? The same brand of ultra-stable Y-type zeolite used in the production of Catalyst-λ! , ,7. llf was added and mixed and mixed for 5 minutes while heating.

Thereafter, in the same manner as in the case of Catalyst-20Elf, ultra-stable Y-type zeolite containing J Owt%, silage was produced and the catalyst components were mutually combined to produce Catalyst-j.

The amount of supported catalyst components and physical properties of catalyst-j are shown in Table-tVC.

Comparative Example (Production of Katana Catalyst-6 Cerium-exchanged Y-type zeolite was not used and the amount of quinoline impregnated was jt, Owt%, ammonium molybdate 7.271 and nickel nitrate 7.5751
A catalyst with palladium-supported amorphous silica and alumina content 'I Owt% and alumina content b Owt% was prepared in the same manner as in the case of producing the catalyst -) except that an aqueous solution containing -g, 7 ml was used. Catalyst-6 was manufactured by manufacturing a carrier and supporting the catalyst components.

Table 1 shows the amount of catalyst components supported and physical properties of Catalyst-6.

(8) Production of catalyst-7 Palladium-supported amorphous silica/alumina was not used and cerium IIIY type zeolite//l1
7 and the amount of quinoline impregnated, ? Cerium was prepared in the same manner as in the production of catalyst-7, except that an aqueous solution containing ammonium molybdate L, 7 g!il- and nickel nitrate 6.621 g-, 7 J, g- was used. Exchange Y to 11 zeolite content 1.!; Owt%
Catalyst-7 was manufactured by manufacturing a catalyst carrier having an alumina content of 5 Owt% and supporting the catalyst components.

Table 1 shows the amount of catalyst components supported and physical properties of Catalyst-7.

(9) Production of catalyst-g Palladium-supported amorphous silica/alumina was not used, and ammonium molybdate di! ,7?
and nickel nitrate L/% Y-type zeolite containing Sumire II
,? Catalyst-g was produced by producing a catalyst carrier with an alumina content of j 7 wt% and supporting catalyst components.

Table 7 shows the amount of catalyst components supported and the physical properties of the catalyst.

(10) Preparation of the catalyst - No impregnation with quinoline solution and ammonium molybdate/j, j f and nickel nitrate/
Aqueous solution A &, 6+n/! containing j, 67! Catalyst-9 was produced by producing a catalyst carrier and carrying catalyst components in the same manner as in the production of Catalyst-/, except that .

Table 1 shows the amount of catalyst components supported and physical properties of Catalyst-9.

<Hydrodesulfurization, hydrocracking reaction> Catalysts-1 to -5 of the present invention and Comparative catalysts-6 to -9 each 1
．． ．． 0? , Arabian heavy atmospheric residual oil (sulfur content j,
? dwt%, 360°C tenth fraction de, /wt%) 1, o,
o g- in a 200 ml volume upper and lower neck shaking type autoclave, and J90C, tbθkp / adG 3
Time hydrodesulfurization and hydrocracking treatments were performed. Removal rate of sulfur content, 3t, reduction rate of oc-10 fraction, middle distillate (tsO
~3boc>yield, and light fraction (3o-tsoC)
The yield is shown in Table-C.

Table - Yu

Claims (6)

[Claims] (1) A carrier made of a mixture of alumina, amorphous silica/alumina, and Y-type zeolite supports iron group metals and platinum group metals of group VIb and group VIII metals of the periodic table, with a specific surface area of 300 to 500 m^. 2/g catalyst, [1] The volume of pores with a radius of 20 to 300 Å is 0.35 ml.
/g or more, [2] Shows a pore distribution with one clear peak at a radius of 20-40 Å and one at a radius of 50-100 Å, [3] The volume of pores with a radius of 20-45 Å is 20-30 Å.
It is in the range of 15-40% of the volume of the 0 Å pore, with a radius of 4
A hydrodesulfurization/hydrocracking catalyst characterized in that the volume of pores with a radius of 5 to 150 Å is in the range of 55 to 85% of the volume of pores with a radius of 20 to 300 Å. (2) The amount of amorphous silica and alumina in the carrier is 2
The catalyst according to claim 1, wherein the content is 0 to 40 wt%. (3) The amount of Y-type zeolite in the carrier is 20 to 40w of the carrier
% of the catalyst according to claim 1. (4) The catalyst according to claim 2 or 3, wherein the amount of amorphous silica/alumina and Y-type zeolite in the carrier is 40 to 70 wt% of the carrier. (5) The catalyst according to claim 1, wherein at least one group VIb metal and at least one iron group metal of group VIII metal are supported on alumina in a carrier. (6) The catalyst according to claim 1, wherein at least one platinum group metal of group VIII metal is supported on amorphous silica/alumina in a carrier.