JPS58138788A - Hydrogenolysis method of heavy oil - Google Patents

Abstract

PURPOSE:To carry out the hydrogenolysis of a heavy oil efficiently with a small amount of hydrogen consumption, by using a catalyst consisting of a specific metal supproted on a carrier consisting of an aluminosilicate subjected to the specific treatment and an inorganic oxide. CONSTITUTION:A crystalline aluminosilicate is first steamed preferably at 540- 810 deg.C, and treated with an aqueous solution of an iron salt preferably under acidic conditions <=1.5pH, washed, and calcined at 300-800 deg.C. The resultant aluminosilicate containing the iron is then treated with a molybdenum compound, e.g. a molybdate, to give preferably 0.5-10wt% MoO3 content in the silicate. A heavy oil is then subjected to the hydrogenolysis in the presence of a catalyst consisting of a metal of Group VIB, preferably W or Mo, and a metal of Group VIII, preferably Ni or Co, supported on a carrier consisting of 20-80% resultant aluminosilicate containing the molybdenum and iron and 80-20% inorganic oxide, preferably alumina sol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for hydrocracking heavy oil, and more specifically, the present invention relates to a method for hydrocracking heavy oil using a catalyst comprising an active ingredient supported on a carrier made of an aluminosilicate and an inorganic oxide that has been subjected to a specific treatment. This invention relates to a method for efficiently hydrocracking heavy oil to convert it into high-value light oil.

In recent years, there has been a global trend toward heavier crude oil, and at the same time,
The demand structure for petroleum is changing, with a tendency for light oil to be in short supply and heavy oil to be in surplus. Therefore, many technologies have been developed to crack down heavy oil and convert it into light oil such as naphtha, kerosene, and diesel oil.

Among these, hydrocracking technology in particular is considered to be very promising because it yields high-quality light oil.

However, traditional hydrocracking technology is limited to kerosene.

It had various drawbacks, such as a low yield of middle distillates equivalent to light oil and high hydrogen consumption.

Therefore, the inventors of the present invention have recently developed a method for hydrocracking heavy oil using a catalyst containing steam-treated crystalline aluminosilicate treated with an iron salt aqueous solution as one of the carrier components (patent application). Specification No. 196972). When this catalyst is used to hydrocrack heavy oil, etc., the amount of carbon deposited is small and the catalyst has good heat resistance, so the reaction can proceed while maintaining high activity for a long period of time. It has the advantage that the yield of middle distillates is also relatively high.

The present invention is a further improvement of the above technology, and is a method that is significantly superior in various respects such as catalyst activity, life, and yield of middle distillates.

That is, the present invention provides a method for hydrocracking heavy oil in the presence of a catalyst, in which a steam-treated crystalline aluminosilicate is treated with an aqueous iron salt solution and then treated with a molybdenum compound. Aluminosilicate 20-0% by weight and inorganic oxide gθ~20% by weight
The present invention provides a method for hydrocracking heavy oil, characterized in that a catalyst comprising a metal belonging to group VIB of the periodic table and a metal belonging to group VIB of the periodic table is supported on a carrier comprising:

Molybdenum is used as a carrier for the catalyst used in the method of the present invention.
Mixtures of iron-containing aluminosilicates and inorganic oxides are used. Here, the molybdenum-iron-containing aluminosilicate is obtained by using crystalline aluminosilicate as a raw material, treating it with steam, then treating it with an aqueous iron salt solution, and further treating it with a molybdenum compound. There are no particular restrictions on the crystalline aluminosilicate used as this raw material, and various materials can be used, but usually the ratio of silica to alumina is 1A6 or more, and Na2
The content should be below 7% by weight, preferably below 7% by weight. Specifically, Khojasite,
Examples include natural zeolites such as mordenite, and synthetic zeolites such as X-type, Y-type, and L-type zeolites. Any of these can be suitably used, but those with a large effective cavity diameter are particularly preferred. Note that if this crystalline aluminosilicate has a ratio of silica to alumina of less than 446 or a Na2O content of more than 10% by weight, the silicate skeleton will be destroyed when treated under strong acidity with a pH of 13 or less. There is a risk of it collapsing. However, when processing under weak acidic or neutral or alkaline conditions with a pH of 75 or more, there is no need to particularly consider the ratio of silica to alumina in crystalline aluminosilicate or the Na2O content.

] Second, the crystalline alumino/licade is treated with steam,
In this case, it is preferable to carry out the treatment in the presence of steam at a temperature of 5g0 to 10°C. Here, the water vapor may be in a flow system, or the crystalline aluminosilicate may be held in a closed container and heated, and self-steaming may be performed using the water contained in the aluminosilicate.

Subsequently, it is necessary to treat the steam-treated crystalline aluminosilicate with an aqueous iron salt solution.

Various salts and complex salts are used as the iron salt aqueous solution, but ferrous chloride and ferric chloride are generally used.

Aqueous solutions of ferrous nitrate, ferric nitrate, ferrous sulfate, ferric sulfate, etc. are used. When treating the above-mentioned steam-treated crystalline aluminosilicate with this iron salt aqueous solution, it is preferable to adjust the pH of the system to acidic, particularly T)H15 or lower. Therefore, it is also effective to add an acid to the system if necessary, and hydrochloric acid, nitric acid, sulfuric acid, etc. are preferably used as such acids. After treatment with an iron salt aqueous solution whose pH was adjusted to /S or less, then washing and drying,
When fired at 300~g00°C, some of the aluminum that makes up the aluminosilicate crystals is eluted,
Iron enters the metal and new chemical bonds are formed.

Other conditions when treating the above-mentioned steam-treated crystalline aluminosilicate with an iron salt aqueous solution are not particularly limited and may be determined as appropriate, but usually at a temperature of 0 to 700 °C,
．． Leave in contact for about 5 to 70 hours. The contacting method may be simply immersing the crystalline aluminolicide in the iron salt aqueous solution, but the purpose can be achieved in a shorter time by stirring or the like.

Further, although such treatment may be performed only once, if it is repeated multiple times, an aluminosilicate with a high iron content can be obtained. Furthermore, it is effective to use ultrasonic waves during the contact treatment.

The iron-containing aluminosilicate obtained by the above treatment is further treated with a molybdenum compound.

Molybdenum compounds that can be used here include:
Various molybdates and molybdenum oxides.

Examples include molybdenum carbonyl.

Further, this treatment can be carried out by various methods and conditions, but generally it is carried out by an impregnation method, a crosstalk method, etc. using a solution dissolved in water or various organic solvents. Furthermore, when using a sublimable compound, the compound can be sublimed for treatment. In the above treatment, care should be taken to ensure that the molybdenum compound is dispersed as uniformly as possible.

The amount of the molybdenum compound to be used may be determined as appropriate depending on various conditions, but preferably the content of MoO3 in the obtained molybdenum-iron-containing aluminosilicate is θS~/,
Qwt%. Note that this treatment with a molybdenum compound must be performed after the aluminosilicate is treated with an aqueous iron salt solution and before the metals of Group VIB or Group 1 of the periodic table are supported.

After carrying out the above treatment, the obtained aluminosilicate was thoroughly washed, and after further drying, 300'C-gooo
By firing at C, the desired molybdenum-iron containing aluminosilicate can be obtained.

On the other hand, the inorganic oxide that constitutes the catalyst carrier together with the molybdenum-iron-containing aluminone oxide mentioned above is added to maintain the physical strength of the catalyst and to enhance its function as a catalyst through appropriate pore distribution. , various types can be used as long as they are suitable for this purpose, but
For example, hydrous oxides such as boehmite gel, alumina sol, and liquor alumina gel are preferably used.

In addition, the mixing ratio of the molybdenum-iron-containing aluminosilicate and the inorganic oxide in the catalyst carrier is: former: latter = 2
0-go: go-20 (wt%), preferably da0-70:60-30 (wt%). If the mixing ratio of the molybdenum-iron-containing aluminosilicate is too small, the yield of the middle distillate will be low. On the other hand, if it is too large, the selectivity of the middle distillate will be low.1.・Hydrogen consumption increases. First, in the catalyst used in the present invention, a metal belonging to Group VIB of the periodic table and a metal belonging to Group 1 of the periodic table are used as the active component to be supported on the carrier. It is necessary to use the Group VIB metal and the Group 1 metal in combination, and the purpose of the present invention cannot be achieved by using only one of them.

Here, the Group VIB metal is preferably tungsten or molybdenum, and the Group 1 metal is preferably nickel or cobalt. Note that seven types of Group VIB metals and seven Group 1 metals may be used, but a mixture of a plurality of metals may also be used.

The supported amount of the above-mentioned active ingredient metal is not particularly limited and may be determined as appropriate depending on various conditions, but usually the metal of Group VIB of the periodic table is 3 to 2 da weight% of the entire catalyst, preferably should be between 3 and 20% by weight, and for Group 1 metals between 07 and 20% by weight of the total catalyst, preferably /! ;-g% by weight.

In order to support the above active ingredient on a carrier, coprecipitation method,
This may be carried out by a known method such as an impregnation method or a kneading method.

Subsequently, the heavy oils to which the method of the present invention can be applied include atmospheric distillation residue oil of crude oil, vacuum distillation residue oil, vacuum heavy gas oil, catalytic cracking residue oil, Bispray kink oil, and tar sand oil. , sierre oil, etc.

Also, /. It can also be used for base oil production.

When carrying out the method of the present invention, a wide range of reaction conditions can be employed, including reaction conditions conventionally employed in hydrogenolysis, but usually the reaction temperature is 350 to 950°C.
C9 reaction pressure SO-200cm2. Hydrogen/raw oil ratio S00~300ON, 113-H2/u-oil, liquid hourly space velocity (LH8V) 0. / ~/ Q hr'-
', preferably θcorl Ohr-'1. Further, hydrogen having a purity of 75 mol% or more is used.

The method of the present invention proceeds by hydrocracking heavy oil using the catalyst described above under the reaction conditions described above.

According to the method of the present invention, hydrogenolysis proceeds efficiently,
A large amount of hydrocracked oil is obtained. Furthermore, the proportion of middle distillates such as lamps and gas oils in the obtained hydrocracked oil is high, and this middle distillate has a low unsaturated content and aromatic content and is of extremely high quality that can be used immediately as a product. . In particular, according to the method of the present invention, the yield of middle distillate / lateral root High degree. Furthermore, the amount of hydrogen consumed during the hydrocracking process is small compared to conventional methods, making it an economically advantageous method.

Therefore, the method of the present invention can be effectively utilized in the field of petroleum refining.

Next, the present invention will be explained in more detail with reference to Examples.

Examples/(1) Preparation of catalyst Na20 content θII wt, %+ S l 02 /
A-e203 3 filtration (mole ratio) Y type zeolite 1o
The ot was placed in a rotary kiln and subjected to self-steaming treatment at 6EC°C for 3 hours. The weight loss at this time was approximately QQvrt%. This steaming zeolite (hereinafter abbreviated as "SHY zeolite J") gθf and concentration 0.2θ mol/13 (D Fe (NO3)a
(') Aqueous solution (pH=10) goo-! The mixture was placed in a three-necked flask and stirred at 50°C for 2 hours. After that, it was suction filtered and further washed thoroughly with ion-exchanged water/θ form at 50°C, dried at gθ°C for 3 hours, and then
It was calcined at 0° C. for 3 hours to obtain iron-containing steaming zeolite (hereinafter referred to as FrF, nee-SHY zeolite). After that +7) Fe -SHY Zeolite powder 757 and ace) Nido1,1 /Ll 2EC-
CK, so-)phthene carbonyl Mo(Co)sg2
The slurry in which gf was dissolved was placed in a 2-volume three-necked flask and stirred at gθ°C for 3 hours. Subsequently, acetonitrile was evaporated from this slurry using a rotary evaporator, and then dried at 720°C for 3 hours.
Of/#f'a, 1tvFcs00'c-ct@rA*
$, IIj3'? to produce molybdenum-iron-containing steaming zeolite (hereinafter referred to as "Mo-F'e-8HY zeolite").
I got it. The composition of this material is Na2O content 0/wt%,
sio,, /Mzo373 (molar ratio), 5j
02/ Feze3”IO, 9 (molar ratio), + 8
102/MoO37θ7 (molar ratio).

On the other hand, aluminum hydroxide was precipitated by reacting an aqueous solution of aluminum chloride with an aqueous solution of sodium hydroxide in an amount 3 times the mole thereof, and after aging at 95° C./g hour, the precipitate was filtered and washed with water to obtain a boehmite gel.

The Mo-Fe-8HY zeolite gel and alumina boehmite gel/g9f were kneaded with 3 Q cc of ion-exchanged water, adjusted to a moisture content suitable for wet extrusion, and molded under a molding pressure of 30 kg/cm2.

It was molded into 3 lengths. Subsequently, it was dried at 720°C for 3 hours,
Further, it was calcined at 300° C. for 3 hours to obtain a Mo-Fe-8HY zeolite-A&03 carrier having a Mo-Fe-8HY zeolite content of 12%.

Next, a concentrated solution of ammonium metatungstate (WO35θOwt%) 20, Otnt
, aqueous solution 64'- containing nickel nitrate/'A9f was added and impregnated, dried at 90°C for 3 hours, and then 550°C
Tungsten/S as metal by firing at ℃ for 2 hours.
/wt%, nickel Qqwt% catalyst was prepared.

The specific surface area of this product was 39 m2/f.

(2) Hydrocracking reaction Catalyst prepared as described above/00. Fill a stainless steel reaction tube with CC and heat at 770°C, 20°C91I.
Atmospheric distillation residue oil (specific gravity/,!
;/l1℃0.9 A 5, 3'13°C1wo2
vo-g%.

S3.9 wt%) to LH8V Q,! ;hr,
Hydrocracking was carried out with a hydrogen/oil ratio of 200 ONm3/KI3-oil. The results are shown in Table 1.

Example The catalyst/p obtained in Example/(1) was charged into a stainless steel reaction tube, and the temperature was raised to 'I/! ;0C, hydrogen partial pressure/35A? /
Hydrocracking was carried out through the residue oil. The results after 500 hours are shown in Table 2.

Comparative Example 1 11) Preparation of catalyst The same procedure as Example/(1) was carried out except that Fe-EIHY zeolite was obtained instead of Mo-Fe-8HY zeolite in Example/(1), and the catalyst was prepared using this. A similar operation was performed. The specific surface area of the obtained catalyst was 37
It was 8m2/9.

(2) Hydrocracking reaction The same operation as in Example/(2) was performed except that the catalyst obtained in step +11 above was used. The results are shown in Table 1.

Comparative Example (1) Preparation of catalyst Molybdenum carbonyl Mo(Co)6 was used in the catalyst prepared in Comparative Example/(1), and molybdenum was added as M2O3/gwt, % content in the same manner as in Example/(]). I forced it. The specific surface area of the obtained catalyst was 367 m 27 t
Met.

(2) Hydrocracking reaction The results are shown in Table 1 except that the catalyst obtained in (1) above was used.

Comparative Example 3 Using the catalyst prepared in Comparative Example 11), hydrogenolysis was carried out under the same conditions as in Example 3. The results are shown in Table 2.

/

Claims (1)

[Claims] (11) Molybdenum obtained by treating steam-treated crystalline aluminosilicate with an aqueous iron salt solution and then treating with a molybdenum compound in a method of hydrocracking heavy oil in the presence of a catalyst. -Iron-containing aluminosilicate 2θ~
A catalyst comprising a metal belonging to Group VIB of the periodic table and a metal belonging to Group Ⅰ of the periodic table is used on a carrier consisting of 20% by weight of an inorganic oxide and 20% by weight of an inorganic oxide. Hydrocracking method. (2) Iron salt aqueous solution has pHi! The method according to claim 1, which is: