JPS58103588A - Hydrogenolysis of heavy oil - Google Patents

Abstract

PURPOSE:To efficiently obtain a large amount of hydrocracked oil, by hydrocracking heavy oil in the presence of a specified catalyst. CONSTITUTION:A crystalline aluminosilate with a silica to alumina ratio of 4.6 or above and an Na2O content of 2.4wt% or below is treated at 540-810 deg.C in the presence of steam, immersed in an aq. soln. (pH 1.5 or lower) of an iron salt such as FeCl2, treated at 0-100 deg.C for 0.5-10hr, washed with water, dried and fired at 300-800 deg.C to obtain an iron-contg. aluminosilicate (A). 3-24wt% Group VIB metal and 0.7-20wt% Group VIII metal of the Periodic Table are supported on a carrier composed of a mixture of 20-80wt% component A and 80-20wt% inorg. oxide (B) such as boehmite gel to obtain a catalyst. Heavy oil is hydrocracked in the presence of this catalyst, at a ratio of hydrogen/oil of 700- 200Nm<3>-H2/kl-oil, liquid hourly space velocity of 0.2-1.0hr<-1> and 350-450 deg.C under pressure of 50-200kg/cm<2>.

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. 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 1I111 structure of petroleum has changed, showing 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, hydrogen specific cracking technology is particularly promising because it yields high-quality light oil.

However, traditional hydrocracking technology is limited to kerosene.

There were various drawbacks such as low yield of middle distillate equivalent to light oil and high hydrogen consumption.

Therefore, the applicant of the present application recently developed a catalyst using a specific crystalline aluminosilicate treated with an iron salt aqueous solution as a carrier (%1 1984-100546@specification)
. When this catalyst is used for hydrocracking of heavy oil,
Because the amount of carbon deposited is small and the catalyst has good heat resistance, the reaction can proceed while maintaining high activity over a long period of time. However, with this catalyst, the yield of middle distillates is still insufficient, and the amount of hydrogen consumed cannot be reduced significantly compared to the conventional method, although it can be reduced slightly.

The purpose of the present invention is to develop a method for hydrocracking heavy oil that provides a high yield of middle distillates and consumes less hydrogen. In the hydrogenolysis method, a carrier consisting of 20 to 80% by weight of iron-containing aluminosilicate obtained by treating steam-treated crystalline aluminosilicate with an aqueous iron salt solution and 80 to 20% by weight of an inorganic oxide is coated with a periodic system. The present invention provides a method for hydrocracking heavy oil using a catalyst supported with a metal belonging to group ⅢB of the table and a metal belonging to group vlT#c.

A mixture of an iron-containing aluminosilicate and an inorganic oxide is used as a support for the catalyst used in the process of the invention. Here, the iron-containing aluminosilicate is obtained by using crystalline aluminosilicate as a raw material, treating it with steam, and further treating it with an aqueous iron salt solution. There are no particular restrictions on the crystalline aluminosilicate used as this raw material, and a variety of materials can be used, but usually the ratio of silica to alumina is 4.6 or more, and the nano content is 2-4% by weight. The content should preferably be 1% by weight or less. Specifically, Khojasite.

Natural zeolite such as mordenite or Y type.

Synthetic zeolites such as Y type and L type can be mentioned. Any of these can be suitably used, but those with a large effective cavity diameter are particularly preferred. In addition, as this crystalline aluminosilicate, the ratio of silica to aluminum is less than 4.6, or the nano-containing material is 2.
If more than -4% by weight is used, there is a risk that the silicate skeleton will collapse when treated under strong acidity with a pH of 5 or less. However, when removing the pH of 5 or more or treating under neutral or alkaline conditions, the alumina of crystalline aluminosilicate is removed by removing Φ
Ratio or Nan.

There is no need to particularly consider the content.

The above-mentioned crystalline aluminosilicage is treated with steam, and in this case, the treatment is preferably carried out in the presence of steam at a temperature of 540 to 810°C. Here, the steam may be in a flow system, or the crystalline aluminosilicate may be held in a closed container and heated, and the water contained in the aluminosilicate may be used to perform 7-luer steaming.

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 base 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 steam-treated crystalline aluminosilicate with this iron salt aqueous solution, the - of the system must be acidified, especially B4 to a pH of 1.5 or lower.
It is preferable to section. Therefore, it is effective to add an acid to the system if necessary. Examples of such acids include hydrochloric acid, nitric acid, and sulfuric acid. When treated with
Iron is eluted and replaced by iron, forming a new crystal structure.

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 100 ° C.
α Leave in contact for about 5 to 10 hours. The contacting method may be simply immersing the crystalline aluminosilicate in an aqueous iron salt solution, but the purpose can be achieved in a shorter time by stirring or the like.

Further, although this 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 aluminosilicate obtained by the above treatment is thoroughly washed, further dried, and then calcined (500 to 800°C).
The desired iron-containing aluminosilicate can then be obtained.

On the other hand, the inorganic oxide that constitutes the catalyst carrier together with the above-mentioned iron-containing aluminosilicate is added to maintain the physical strength of the catalyst and enhance its function as a catalyst through appropriate pore distribution. Various materials can be used as long as they are compatible with the requirements, such as boehmite gel.

Hydrous oxides such as alumina gel and silica-alumina gel are preferably used.

Further, the mixing ratio of the iron-containing alkali-based silicate and the inorganic oxide in the catalyst carrier is: former = latter = 20 to 80:8
0~20 (weight i1%), preferably 40~70:60~
3o (% by weight). If the mixing ratio of the 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 and the amount of hydrogen consumed will be large.

Next, in the catalyst used in the present invention, as the active component to be supported on the carrier, a metal belonging to Group VIB of the periodic table and a metal belonging to the first layer are used. This VI
It is necessary to use the Group B 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 metals include tungsten and
or molybdenum is preferred, and the Group 1 metal is preferably nickel or cobalt. Incidentally, one kind each of Group 1 metals and Group 1 metals may be used, but a mixture of a plurality of metals may also be used.

The supporting device for the above-mentioned active ingredient metal is not particularly limited and may be determined as appropriate depending on each spear condition, but usually metals from group 71B of the periodic table are preferably used in a proportion of 3 to 24 times the entire catalyst. should be between 8 and 20 percent, and for Group 1 metals, it should be between 17 and 20 percent by weight, or 5 to 8 percent by weight, of the entire catalyst.

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.

Subsequently, as heavy oil to which the method of the present invention can be applied, atmospheric distillation of crude oil 1i! 4 residue oil, vacuum distillation sill residue oil, vacuum distillation J1 residue oil, catalytic cracking residue oil, visbreaking oil, tar sand oil, shale oil, etc.

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 450°C.
1 reaction pressure 50-200 hours/-1 hydrogen/raw oil ratio 700
~20001 m'-Hz/U-oil, liquid time-space velocity (L
H8V) (L2~t0hr-"), and hydrogen with 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,
Multiple hydrocracked oils are 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 distillates is 10% higher than when using iron-free dealuminated zeolite (tlBY type zeolite) or iron-containing aluminosilicate zeolite that has not been treated with steam. To a high degree.

Furthermore, the consumption of hydrogen during the hydrocracking process is less than that of 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 using examples.

Example 1 Preparation of tlj catalyst The catalyst was charged and subjected to steaming treatment at 680° C. for 3 hours. The weight loss at this time was about 20 wt%.

This steaming zeolite (hereinafter abbreviated as "8HY zeolite") 80? and concentration (L20mok/tO
7s (101) @Aqueous solution (pH-tO)aoo*
was placed in a three-necked flask with a volume of 1 and stirred at 50°C for 2 hours. After that, it was suctioned, washed thoroughly with 10 tons of ion-exchanged water at 50°C, dried at 80°C for 3 hours, and then calcined at 450'C for 3 hours to produce iron-containing steamed zeolite (hereinafter referred to as iron-containing steamed zeolite). [1.-8HY zeolite] was obtained. The composition of this product was NaaO content (L10vt%, 5tos/mu40s7.8 (mole ratio), 8102/F@2014 A4 (mole ratio).

On the other hand, aluminum hydroxide was precipitated by reacting an aqueous aluminum chloride solution with an aqueous sodium hydroxide solution in an amount 5 times the molar amount, and after aging at 95°C for 18 hours, the precipitate was filtered and washed with water to obtain a boehmite gel.

The above re-S HY 4 olide 67g and alumina boehmite gel 189? Add 5 occ of ion-exchanged water and knead with IJL to make the moisture content suitable for hot extrusion molding! #It was moistened and molded to a diameter of 1-9 and a length of 5 cm at a molding pressure of 501 Cg/cd. Subsequently, it was dried at 120°C for 5 hours, and further dried at 500°C.
After baking for 5 hours, Fs-B HY containing zeolite
A 120s carrier containing 60 wt% Fe-8HY zeolide was obtained.

Next, a concentrated ammonium metatungstate solution (WO, SαQ wt%) 2αOIL/ was applied to the carrier 75f.

64ml of aqueous solution containing nickel (14.9) in 61'J#
After adding and impregnating it, it was dried at 90°C for 3 hours, and then fired at 550°C for 2 hours to form tungsten as a metal.
A catalyst containing h 1 vt% and nickel l 9 wt% was prepared. The specific surface area of this product was 578w1/l.

(2) Hydrocracking reaction 100 cc of the catalyst prepared above was filled in a stainless steel reaction tube at 410°C and 420°C.

Atmospheric distillation residue oil (specific gravity 15/4℃ α965゜545
℃+92 vo1%, S! h 9 wt%) to r, ngva 5 hr-”, hydrogen/oil ratio 2000
Hydrogenolysis was carried out through 1 liter of 1-o1 tr. The results are shown in Table 1 and Figure #g1.

Comparative Example 1 (Wataru) Preparation of Catalyst The same treatment as in Example 1 was carried out except that hydrochloric acid of pH 1O was used instead of the Mows aqueous solution in Example 1 (1). 1 vt
%, Si pseudo/A40.9.5 (molar ratio) dealuminated Y-type zeolite was obtained. A catalyst was prepared in the same manner as in Example 1 (!).

(2) Hydrocracking reaction Example 1 except that the catalyst obtained in (1) above was used.
A hydrogenolysis reaction was carried out in the same manner as in (2).

The results are shown in Table 1 and Figure 1.

Comparative Example 2 0) Preparation of Catalyst A catalyst was prepared in the same manner as in Example 1 (1) except that in Example 1 (tl), the steaming treatment was not performed.

(2) Hydrocracking reaction Example 1 except that the catalyst obtained in (1) above was used.
A hydrogenolysis reaction was carried out in the same manner as in (2).

The results are shown in Table 1 and Figure 1.

Table 1

[Brief explanation of the drawing]

FIG. 1 shows Example 1. 2 is a graph showing the relationship between conversion rate and middle distillate selectivity in Comparative Example 1 and Comparative Example 2. Procedural amendment sound (spontaneous) January 51, 1980 Commissioner of the Japan Patent Office Kazuo Wakasugi t Indication of the case Patent application 1982-196972 2. Name of the invention Process for hydrocracking of heavy oil 5. Person making the amendment Related: Patent applicant Heavy Oil Countermeasures Technology Research Association 4, Agent Address: 1-1-10 Kyobashi, Chuo-ku, Tokyo 104 A grasp of the detailed explanation of the invention in the specification subject to amendment to ``Alumina Sol'' [correction] do. (2) Page 9, line 4 [α2~t, Ohr-”
Correct J to [α2~10hr-'J. (3) "Alumina boehmite gel" on page 11, lines 9-10 is corrected to "boehmite gel."(that's all)

Claims (2)

[Claims] (1) In a method of hydrocracking heavy oil in the presence of a catalyst, 20 to 80% by weight of iron-containing aluminosilicate obtained by treating steam-treated crystalline aluminosilicate with an aqueous iron salt solution and inorganic oxide. A method for hydrocracking heavy oil, characterized in that a catalyst comprising a metal belonging to Group 1B of the periodic table and a metal belonging to Group 1 of the periodic table is supported on a carrier having a weight of 80 to 20%. (2) The method according to claim 1, wherein the iron salt aqueous solution has a concentration of atS or less.