JPS5834891A - Heavy oil catalytic cracking method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for catalytic cracking of heavy oil.
This invention relates to a method capable of obtaining high octane number gasoline and middle distillates in high yield.

Traditionally, silica-alumina compounds have been widely used as catalysts for fluid catalytic cracking. In recent years, silica-alumina or alumina blended with zeolite have shown excellent cracking activity and durability. It has come to be widely used as a product.

However, although the above-mentioned catalysts made of silica-alumina or alumina mixed with zeolite exhibit high cracking oil properties in the catalytic cracking of heavy oil, they have the disadvantage that the obtained gasoline fraction has a low octane number. Also, this catalyst uses kerosene.

Considering the recent petroleum situation where the yield of middle distillates equivalent to light oil etc. is not sufficient, especially middle distillates are in short supply.
A new catalyst is desired, especially a catalyst-on generation method that provides a high yield of middle distillates.

Therefore, the present inventors conducted a study on heavy oil using the above-mentioned conventional catalyst. We have carried out extensive research in order to overcome the drawbacks of the catalytic cracking method and develop a method that can obtain both high-octane gasoline fractions and middle distillates in high yields. the result,
In the catalytic cracking of heavy oil, we discovered that the objective can be achieved by using a catalyst containing crystalline aluminosilicate zeolite treated with a solution containing iron ions! Nine.

The present invention was completed based on this knowledge.

That is, the present invention provides a method for catalytically cracking heavy oil using a solid catalyst, in which the solid catalyst is treated in an acidic iron ion-containing port and consists of a nine-crystalline arunosilicate zeolite and an inorganic oxide. The present invention provides a method for catalytic cracking of heavy oil, which is characterized by It is prepared by kneading the iron ion-containing solution and an inorganic oxide commonly used in catalysts, followed by molding, drying, and sintering. Here, the crystalline aluminosilicate zeotite, which is one of the raw materials for the solid catalyst, can have various compositions, but usually the ratio of silica to alumina is 46 or more, and N&:
It is sufficient that the content of 0-containing particles is 2.4% by weight or less, preferably 1% by weight or less.
There are other examples such as Kanase Nana Otei F. In the solid catalyst used in the method of the present invention, it is necessary to further treat the above-described crystalline albinosilicate zeolite with an iron ion-containing solution, dry it, and calcinate it. Here, as the iron ion-containing solution, various iron salts and complex salt solutions are used, but generally ferrous chloride, ferric chloride, and ferrous nitrate are used.

Aqueous solutions of ferric nitrate, ferrous sulfate, ferric sulfate, etc. are used. Further, this iron ion-containing solution must be adjusted to an acidic region. Particularly preferred is one whose IPH is adjusted to 2 or less. In addition, in order to adjust the pH of this iron ion-containing solution to 2 or less, dihydrochloric acid, nitric acid, sulfuric acid, etc. may be added as necessary.

Crystalline arsenosilicate zeolite can be treated with a solution containing iron ions by various methods, but usually at a temperature of 0 to 100°C for 15 to 10 minutes.
The zeolite may be immersed in an iron ion-containing solution for about an hour. It is also effective to irradiate the mixture with stirred water or ultrasonic waves, if necessary. The content of iron ions in the crystalline T# senosilicate zeolite treated here is not particularly limited, but the content of iron ions in the zeolite is 5%.
It is preferable to set it to about NtO weight % (m, o, conversion).

On the other hand, the inorganic oxide constituting the other part of the solid catalyst used in the method of the present invention is a porous inorganic oxide used in ordinary catalytic cracking. As this inorganic oxide, for example, alumina such as boehmite gel and alumina sol, silica such as silica sol, or silica-alumina can be used.

In the solid catalyst used in the method of the present invention, the mixing ratio of the crystalline aluminosilicate zeolite treated with the iron ion-containing solution and the inorganic oxide described above may be determined as appropriate depending on the type of zeolite or inorganic oxide or the purpose of use. The zeolite storage inorganic oxide is usually 15 to 70%
s97-i.

(weight ratio).

The method of the present invention performs catalytic cracking of heavy oil using the above-mentioned solid catalyst. Here, as heavy oil to be catalytically cracked,
There are no particular restrictions, and various options are possible, but - for example, crude oil's atmospheric distillation residue oil, vacuum distillation residue oil, 1 heavy gas oil, 1 vacuum gas oil, 1 shale oil, and hydrocarbon oil derived from tar sands. etc. Further, when catalytically cracking heavy oil according to the method of the present invention, a wide range of reaction conditions conventionally employed in catalytic cracking may be employed. The specific reaction conditions vary depending on the type of raw material oil and cannot be unambiguously determined, but usually the reaction temperature is 400 to 65°C.
Preferably, the temperature is 0° C. and the reaction pressure is reduced to several hundred atmospheres.

According to the present invention, it is possible to obtain gasoline with a high octane number in a higher yield than with conventional methods, and at the same time, the yield of middle distillates corresponding to kerosene, gas oil, etc. can be also lowered. It is expensive, and the amount of Konik produced is also small. Moreover, since the solid catalyst used here has high heat resistance, metal resistance, and sulfur resistance, it can maintain high catalytic activity for a long period of time even if catalytic cracking is performed under severe conditions.

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

Next, examples of the present invention will be shown.

Example 1 1alO content' 4wt% e company oV pigeon o, (+
lk ratio) i6 crystalline quality aluminosilicate zeolite (
Y-type zeolite) 100) and an aqueous solution (pmas) of Th (No) with a concentration of 125 mol/l
was placed in a three-hole flask with IA capacity, stirred at 50°C for 2 hours, then suction filtered, thoroughly washed with water 104 at 50°C, dried at 50°C for 4 hours, and then stirred at 50°C for 2 hours.
Crystalline aluminosilicate F zeolite containing iron (Mh@O content (125vt%) was calcined at 0°C for 3 hours.
, 810s/jk&011 (+14 compared)
1 a S @ company 0 @ 7'1lasOs (molar ratio) 2
42) was obtained.

On the other hand, an aqueous solution of aluminum chloride and an aqueous solution of sodium hydroxide in an amount 5 times the molar amount were reacted, and the aluminum hydroxide was precipitated and aged for 10 hours at <'') spa° C. to obtain a boehmite gel.

Next, the above iron-containing crystalline aluminosilicate zeolite (h-w zeolite) 100).

Boehmite gel 960t and silica sol (trade name Nisnortex-0, Nissan Chemical-g) ssoot were kneaded and molded to a diameter of 1 cm using a wet extrusion molding machine.
It was dried at 20°C for S hours and further calcined at 500°C for S hours to obtain an IF*-HY zeolite content of 1 (L5vt% h
- Niwaze No. 54) - 810g of Al40m'' catalyst was prepared.The specific surface right of this was 240i/i.

Next, the above catalyst 4? was filled into a glass reaction tube, and 48
Desulfurized vacuum gas oil at 2℃ and 1 atm (specific gravity 15/4℃ αa
sos; Boiling point range: 256°C, 79°C.

Catalytic cracking was carried out by passing 1 liter of sulfur content (cL 15%) through the reaction tube for 5 minutes at 10⁵ (LH3V 4 hr⁻”).

The results are shown in Table 1 - Comparative Example 1 In Example 1, instead of 1-MY zeolite, M
alO content a 4 vt %, 1 illies/AT
Catalytic cracking of desulfurized vacuum gas oil was carried out under the same conditions as in Example 1, except that crystalline arunosilicate zeolite (Y-type zeolite) having Os (molar ratio) of 56 was used. The results are shown in Table 1.

Table 1 Procedural Amendment (Voluntary) September 22, 1980 Haruki Shimada, Commissioner of the Japan Patent Office, Indicated Patent @ 56-151622 2 Name of Invention Method for Catalytic Cracking of Heavy Oil 5 Person Who Makes Amendment Related: Contents of the amendment in column 4 of the detailed description of the invention in the specification of patent applicant Idemitsu Kosan Co., Ltd. (1) On page 5 of the specification letter, lines 15 to 18: ...Ndo Synthetic Zeo 1
．． 3.・]-Wa-) Yes. Specifically, natural zeolites such as zeolite and mordenite, or X-type, Y-type, and L-type.

Synthetic zeolites such as ZSM ill can be used. ” is corrected.

(2) On page 4, lines 6 and 7, “It is particularly preferable that the number is 11H2 or less” is changed to “Generally #ipH2
Hereinafter, it will be corrected to h0, especially those whose pH is adjusted to 1 or less.

+31 The following sentence is added after Table 1 on page 9.

“Example 2 Nano content (L4fi%, aiog/AJ40g
('!' k ratio) 6 crystalline aluminosilicate zeolite) (111Y type zeolite) 4 oaf in patch type rotary kiln (inner diameter 100 - 9 length 60IyI)
The mixture was heated with a heater for 1 hour and 40 minutes while rotating, and the temperature was raised to 220°C. The temperature was further held at 22G"C for 2 hours, and then raised to 810"C over 5 hours, self-steamed at 810"C for 5 hours, and then allowed to cool to obtain steam-treated HYfil zeolite (sHy zeolite). .

Next, put 200p of the above 8HY zeolite into a glass three-neck flask with a volume of 2, and add nitric acid to a 10(Not)s aqueous solution with a concentration of 01 mol/l adjusted to 8.
st was added, and the mixture was treated at 50° C. for 2 hours and 1 hour with stirring.

Thereafter, it was suction filtered, further washed with water 201 at 50°C, dried at 50°C for 4 hours, and then calcined at 500°C for 3 hours to obtain Tetsuhoyu zeolite) (Thkawa zeolite). . 310 of this thing! /bou03 (molar ratio) is 1mu2
．． 5i07?5120B (%le ratio) was 4&2. Next, the above hEMY zeolite 50? and boehmite gel 870F obtained in Example 1,
It was molded to a diameter of 1 m using a wet extrusion molding machine. followed by 12
It was dried at 0° C. for 5 hours and further calcined at 500° C. for 5 hours to prepare a 'h-type zeolite-alumina catalyst having a Th8HY zeolite content of 2α5fi%. The specific surface of this item was 2s2?11//P.

Catalytic cracking of desulfurized vacuum gas oil was carried out under the same conditions as in Example 1 using the catalyst 4f. The results are shown in Table 2.

Comparative Example 2 Example 2 5 tons of the obtained SHY heptiothiolide and 870 tons of the boehmite gel obtained in Example 1 were kneaded and molded into a wet extruder having a diameter of 1 mm. Subsequently, it was dried at 120''C for 3 hours and further calcined at 500C for 5 hours to prepare a wave zeolite-alumina catalyst having an 8HY-4' olide content of 2α3 wt%.

Next, desulfurized vacuum gas oil was subjected to catalytic cracking under the same conditions as in Example 1 using the catalyst 4F-. The results are shown in Table 2.

Comparative Example 3 98H obtained in Example 2! Zeolite) 100) was placed in a 2-volume glass three-neck flask, 1000 ml of A2N hydrochloric acid was added to the colander, and the mixture was stirred at 95° C. for 2 hours to proceed with dealumination.

Thereafter, it was filtered by suction, further washed with 20L of water at 50°C, and then dried at 120°C for S hours. Then 5θO℃
Zeolite dealuminated by calcining for S hours at
AL) was obtained. This stuff stow/A140@(
molar ratio) was 1t, d.

Next, the above DAL 50 F and the bean obtained in Example 1! Itogel 87o? The mixture was kneaded, molded into a diameter of 1 mm using an FHI extruder, squeezed and dried at 120"C for 5 hours, and then fired at soo"C for 3 hours to obtain a DAL with a Tsum L content of 2 (L1vt%). - Alumina catalyst was manufactured by liJ.

Catalytic cracking of desulfurized vacuum gas oil was carried out under the same conditions as in Example 1 using Catalyst 4F. The results are shown in Table 2.

Comparative Example 4 The 8HY zeolite (200) obtained in Example 2 was placed in a glass three-necked flask with a capacity of 2, and concentrated Ha 1% A// to N1 (moss) adjusted to 11a8 with nitric acid was added.
s Aqueous solution t41 was added and treated at 50°C for 2 hours with stirring. After that, suction filtration was carried out, and further water Va at 50°C was
After washing at 50°C, drying at 50°C for 4 hours,
C. for 3 hours to obtain M1-containing zeolite (Iiii [zeolite)]. 810 of this thing! /AjaOs
(molar ratio) is 1t7, JiiO1/NIO(+ J
k ratio) was sta.

Next, 870f was anointed to this crucian carp zeolite) 50) and the boehmite thorn obtained in Example 1, and it was molded into a straight lit part by wet extrusion molding, followed by drying at 120°C for 5 hours, and then A summer M4 zeolite F content of 2 (LQ-Zeolite F-Arsena catalyst) was prepared by calcination for 5 hours at soo'e.

Catalyst 4 above? Catalytic cracking of desulfurized vacuum gas oil was carried out under the same conditions as in Example 1. The results are shown in Table 2.

Example 3 ThaBlr-41 obtained in Example 2) 50)
into a three-necked flask and add 25% lanthanum nitrate A/l.
400ml of aqueous solution (1ft of PHI O by adding nitric acid)
) and stirred at 80°C for 5 hours to perform ion exchange treatment. After that, I was happy with suction, and after washing with 18L of water, I
It was dried at 20°C for 5 hours, and then calcined for 5 hours at a
Zeolite) is obtained, and this -o3 containing turtle is t5-
Attack, 810 years/to pigeon (mole ratio) is 115.8bo 3/h1
The molar ratio was 49.8.

Next, the above-? 5Elff Zeolite 50? and boehmite gel 870 obtained in Example 1? The mixture was kneaded and formed into a diameter of 1 mm during wet extrusion molding, followed by heating at 120°C.
Dry at 500℃ for 5 hours, then bake at 500℃ for 5 hours.
Th5l [fY zeolite content 2 (LOvt% - m
A zeolite-alumina catalyst was prepared.

Catalyst 4 above? Table #I2 shows the results of catalytic cracking of desulfurized vacuum gas oil using the same conditions as in Example 1.

Example 4 1 & Goose 0 content a4wt%, 8LO Maro/Hato 0 @ (%
crystalline aluminosilicate zeolite (H
Y-type zeolite) 400) was placed in the batch type rotary kiln used in Example 2 and heated with a heater while rotating.
The mixture was heated over a period of 40 minutes, and the temperature was raised to 220°C.

Further held at 220°C for 2 hours, followed by 1 hour r#4JS
The temperature was raised to 540°C over 0 minutes, self-steamed at 540°C for 5 hours, and then allowed to cool to obtain 8HY zeolite.

Next, put this IIHY Ceolite 150) into a glass three-necked flask with a capacity of 2, and add 1500ml of +12N hydrochloric acid.
was added and treated at 95° C. for 2 hours with stirring. Thereafter, it was subjected to WK filtering, and then thoroughly washed with water 201 at 50°C, and then dried at 120"C to obtain Dmu L-1. Thereafter, the above-mentioned self-steaming - Item 1 treatment - Repeat drying twice.
40s (+k ratio) z6) was obtained.

Subsequently, the above pmu
log)s *Solution 800d! was added and treated with stirring in sa"c for 2 hours. After that, it was suction filtered, further washed with 10 tons of water at 50°C, dried at 50'C for 4 hours, and then treated in soo"c. Bake for 5 hours to obtain Tsum TJ (y/Arashi) containing iron. This thing 810
27 pigeon Os (molar ratio) #i1 hair o1 飄0v-01 (molar ratio) was 410.

Next, the above hTJAXa 50 f and the boehmite gel 1960 f obtained in Example 1 were kneaded, molded into a diameter of 1 mm using an extruder, dried at 120°C for 5 hours, and then baked at SOO°C for S hours. What about lung content? , 8w
t%q) Preparation of Th wind-alumina catalyst Catalytic cracking of desulfurized vacuum gas oil was carried out under the same conditions as in Example 1 using the above catalyst 4F. The results are shown in Table 2.

Claims (1)

[Claims] 1) A method for catalytically cracking heavy oil using a solid catalyst, characterized in that the solid catalyst is composed of crystalline aminosilicone zeolite and inorganic oxide treated with an acidic iron ion-containing solution. A method for catalytic cracking of heavy oil.