JP3479783B2 - Additive for fluid catalytic cracking catalyst of heavy oil - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to relates to a fluid catalytic cracking (FCC) catalysts additive for heavy oil. The heavy oil referred to in this specification has a boiling point of 650 ° F (343 ° C).
It means a hydrocarbon oil containing the above heavy components. As such heavy oil, various crude oils, atmospheric distillation residual oils of those crude oils, vacuum distillation residual oils, solvent-depleted oils, solvent-depleted oils asphalt, shale oil, tar sand oil,
In addition to non-distillate oils such as coal liquefied oil, distillate oils such as HGO (normal pressure heavy gas oil) and VGO (vacuum gas oil), and mixtures of these distillate oils and the non-distillate oils can be mentioned. .

[0002]

2. Description of the Related Art Various methods are known as a method for cracking heavy oil to obtain light oil, and a typical method is fluid catalytic cracking (FCC). In such catalytic cracking of heavy oil, one of the important issues is how to obtain light oil in good yield, and many studies have been made to solve the problem. As one method for improving the yield of light oil, it is known to mix an additive having an action of promoting the decomposition of heavy components in heavy oil with a catalyst for cracking. Conventionally commonly used additives have a SiO ₂ content of 60% by weight.
The oxide that is higher and forms the active ingredient is alumina. However, in the case of such a complex oxide having a high SiO ₂ content, when it is added to a catalyst for cracking heavy oil and subjected to a reaction, it shows high initial activity, but since it has poor hydrothermal stability, There is a problem that the equilibrium activity gradually decreases due to contact with steam existing in the reaction system, and as a result, the yield of light oil also decreases. Further, when alumina is the main component, there is a problem that coke is often deposited on the catalyst during the reaction and the catalytic activity is lowered.

[0003]

[0008] The present invention has a high decomposition activity against heavies in the heavy oil, together with the also immediately in terms of hydrothermal stability, even less heavy oil of coke deposition
It is an object of the present invention to provide an additive for a fluid catalytic cracking catalyst .

[0004]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, according to the present invention, zeolite and porous
Additive for fluid catalytic cracking catalyst composed of inorganic oxide
Yes, silica-alumina, clay and silica particulate mixture
And the silica content in the silica-alumina is 1
0 to 30% by weight of the silicon contained in the mixture.
The content should be 10 to 60% by weight in terms of SiO2.
Provided are the aforementioned additives characterized . Also according to the invention
A stream composed of zeolite and porous inorganic oxide.
Additive for dynamic catalytic cracking catalyst, silica-zirconia
And a particulate mixture of clay and silica.
Silica content in Luconia is 10 to 30% by weight,
The content of silicon contained in the mixture is equivalent to SiO2
10 to 60% by weight of said additive
Will be provided.

The additive for fluid catalytic cracking catalyst of heavy oil of the present invention (hereinafter, also simply referred to as additive) is a silica-containing composite oxide ( silica-alumina or silica-zirconia ).
contains. Sheet Rica - For alumina, the silica content is 10 to 30 wt%, preferably the use of a range of 10 to 20 wt%. If the silica content is more than this range, the hydrothermal stability of the additive will deteriorate, while
When the amount is less than the above range, the decomposition activity of the heavy component becomes low. The silica-alumina used in the present invention is represented by the physical properties of its calcined product, and its surface area is usually 150-4.
50 m ² / g, preferably 200~350m ² / g, its pore volume is usually, 0.2~1.5cc / g,
It is preferably 0.5 to 1.2 cc / g. Further, as the silica-alumina, it is preferable to use one having a structure in which alumina is a nucleus and silica is bonded to the surface thereof in a layered manner.
In the case of silica-zirconia, the silica content is 10
Preference is given to using those in the range of 30% by weight, preferably 10 to 20% by weight. If the silica content is more than this range, the hydrothermal stability of the additive will be poor, while if it is less than the above range, the decomposition activity of the heavy component will be low. The silica-zirconia used in the present invention is represented by the physical properties of its fired product, and its surface area is usually 100 to 400 m.
² / g, preferably 120 to 350 m ² / g, and the pore volume thereof is usually 0.1 to 1.0 cc / g, preferably 0.2 to 0.8 cc / g. Further, as the silica-zirconia, it is preferable to use one having a structure in which zirconia is a nucleus and silica is bonded to the surface thereof in a layered manner.

Examples of clay include kaolin, bentonite,
Although there is wood knot clay and the like, kaolin is preferably used. Generally, those containing one or more clay minerals such as kaolinite, dickite, nacrite, halloysite, and hydrohalloysite as a main component are used.

In order to preferably produce the additive of the present invention,
Clay and silica-containing composite oxide gel are added to the silica sol liquid and stirred uniformly to form a dispersion liquid. In this case, the average particle size of the clay is 1 to 5 μm, preferably 2 to 3 μm. The average particle size of the silica-containing composite oxide is 1 to 10 μm.
m, preferably 3 to 7 μm. The total solid content concentration in the dispersion is 10 to 50% by weight, preferably 20 to 3
It is 0% by weight. The dispersion thus obtained is then spray dried. The drying temperature in this case is 180 to 30.
The temperature is 0 ° C, preferably 200 to 270 ° C. By this spray drying, the additive of the present invention is obtained in powder form. The average particle size of this powder is 50-80 μm, preferably 55-7.
It is 0 μm. The dried product thus obtained is, if necessary, 300 to 700 ° C., preferably 400.
The powdery additives can be used by firing at a temperature of up to 600 ° C., and these powdery additives can be molded by extrusion molding or the like, if necessary, to obtain molded products in the shape of granules, spheres, cylinders, rods, etc. You can also do it.

In the additive of the present invention, the content of the silica-containing composite oxide is 5 to 70% by weight, preferably 1
The content of clay is 0 to 60% by weight, and the content of clay is 10 to 70% by weight, preferably 20 to 60% by weight. The content of silica is 10 to 30% by weight, preferably 15 to 25% by weight. Further, in the additive of the present invention, the content of total silicon, calculated as SiO ₂ weight, 10 to 60 wt%,
It is preferably specified in the range of 20 to 50% by weight. If the total silicon content is more than the above range, the hydrothermal stability of the additive will be poor, while if it is less than the above range, the decomposition activity for heavy components will be reduced.

[0009] The additive of the present invention exhibits high equilibrium decomposition activity for heavy components in heavy oil and at the same time exhibits high hydrothermal stability, and its equilibrium decomposition activity is maintained at a high level even after long-term use. To be done. Additives of the present invention, Ru can be used by mixing into a fluidized catalytic cracking catalyst of the slave come known heavy oil.
The FCC catalyst is composed of a porous inorganic oxide and zeolite, and silica-alumina, silica-zirconia, silica-magnesia, etc. are used as the porous inorganic oxide. The additive of the present invention is particularly an FC composed of zeolite, silica, alumina and kaolin.
It is preferably applied to C catalysts. The amount of the additive of the present invention added to the FCC catalyst is 2 to 30 parts by weight, preferably 4 to 20 parts by weight, based on 100 parts by weight of the FCC catalyst.

[0010]

The additive of the present invention has a high cracking activity for heavy components in heavy oil, particularly heavy components having a boiling point of 650 ° F or higher, and a light oil having a boiling point of 650 ° F or lower. (Gasoline and middle distillates) are given in high yield. Moreover, the additive of the present invention has excellent hydrothermal stability, and even when contacted with steam,
The equilibrium activity does not drop sharply. Special
To, shea silica - additives with zirconia has the advantage that coke deposition is small.

[0011]

EXAMPLES Next, the present invention will be described in more detail by way of examples.

Reference Example 1 (Preparation of SiO ₂ -Al ₂ O ₃ ) 2N ammonium hydroxide aqueous solution was added to 7000 g of aluminum nitrate aqueous solution (pH 3) having Al ₂ O ₃ concentration of 1.3 wt% to prepare water having pH 8.2. A water slurry containing aluminum oxide was obtained. On the other hand, the SiO ₂ content is 8.5w
2N sulfuric acid was added to 170 g of a t% aqueous solution of water glass (pH 12) to adjust the pH to 3.0 to obtain a silica sol liquid. Next, the aqueous slurry of aluminum hydroxide obtained above was added to and mixed with this silica sol liquid with stirring, and 2N ammonium hydroxide was added to the obtained mixture.
The pH was adjusted to 8.2.

Then, the mixture thus obtained was aged at 60 ° C. for 3 hours to gelate the silica sol contained in the mixture to obtain a gel in which silica gel was adhered and bonded to the surface of aluminum hydroxide particles. The gel was separated from the liquid, washed with water, and filtered. The gel thus obtained was used as an additive component. SiO in this gel
_{The 2} / Al ₂ O ₃ weight ratio was 0.11, and its SiO ₂ content was 10 wt%. In addition, the gel is 120 ℃
A part of the dried particles dried in (4) was calcined at 500 ° C. for 3 hours. The calcined product had a surface area of 230 m ² / g and a pore volume of 1.2 cc / g.

Example 1 (Preparation of Additive A) A water glass aqueous solution having a SiO ₂ content of 8.5 wt% (p
2N sulfuric acid was added to 1200 g of H: 12) and the pH was adjusted to 3 to obtain a silica sol. Then, to 1450 g of this silica sol liquid, 102 g of kaolin and 306 g of the SiO ₂ —Al ₂ O ₃ gel obtained in Reference Example 1 in terms of dry weight.
Add and disperse evenly, then spray-dry, average particle size 6
0 μm of additive A was obtained. The composition of this additive A is as follows: silica-alumina 60 wt%, kaolin 20 wt%
% And silica 20 wt%. The total silicon content was 36 wt% in terms of SiO ₂ .

Example 2 (Preparation of Additives B to F) In Example 1, S prepared in the same manner as in Reference Example 1 was used.
Additives B to F were prepared in the same manner except that silica alumina having different iO ₂ content was used and the amounts of silica sol solution, kaolin, and silica-alumina were variously changed. The composition is shown in Table 1 together with the composition of the additive A obtained in Example 1.

Application Example 1 In order to perform a performance test of the additives obtained in Examples 1 and 2, the additives were uniformly mixed with the FCC catalyst, and then the catalyst mixture was subjected to a microactivity test (MAT) apparatus. Using the same raw material oil and the same conditions, the fluid catalytic cracking reaction was performed. The composition of the FCC catalyst is as shown in Table 1,
The amount of the additive added to the FCC catalyst was 10 parts by weight with respect to 100 parts by weight of the FCC catalyst. As a comparative reference, it was carried out also when the additive was not added.
Desulfurized VGO was used as the raw material heavy oil. Also,
Prior to testing, the catalyst mixture consisting of FCC catalyst and additives was calcined at 650 ° C. for 1 hour and then treated at 100 ° C. for 16 hours in 100% steam atmosphere. Furthermore, in order to carry out a hydrothermal stability test of the additive, the additives before and after the steam treatment were reacted with the additive alone in a MAT apparatus. The results are shown in Table 2.

The fluid catalytic cracking conditions in the above test were as follows. (1) Reaction temperature: 520 ° C. (2) Reaction pressure: Normal pressure (3) Catalyst / oil ratio: 2.5 to 4.5 wt / wt (4) Contact time: 32 hr ⁻¹

The conversion, LCO yield, and
Coke yield and hydrothermal stability are defined by the following equations. Further, the LCO yield and the coke yield are values at a conversion rate of 55 wt%. (1) Conversion (wt%) = (A−B) / A × 100 A: Weight of feedstock B: Weight of fraction with boiling point of 221 ° C. or higher in produced oil (2) LCO yield (wt%) = C / A × 100 C: LCO in produced oil (boiling range: 221 to 343 ° C.)
(3) Coke yield (wt%) = D / A × 100 D: Coke weight deposited on the catalyst mixture (4) Hydrothermal stability (%) = Conversion after steam treatment / Before steam treatment Conversion rate x 100

[0019]

[Table 1] * A comparative example is shown.

[0020]

[Table 2] * A comparative example is shown. ** A reference example is shown.

Reference Example 2 (Preparation of SiO ₂ -ZrO ₂ ) ZrO ₂ aqueous solution containing 1.5 wt% ZrO ₂ zirconyl nitrate (p
An aqueous 2N ammonium hydroxide solution was added to 6000 g of H1.5) to obtain a water slurry containing zirconium hydroxide having a pH of 8.2. On the other hand, the SiO ₂ content is 8.5w
2N sulfuric acid was added to 1000 g of a t% aqueous solution of water glass (pH 12) to adjust the pH to 3.0 to obtain a silica sol liquid. Next, to this silica sol liquid, while stirring, the water slurry of zirconium hydroxide obtained above was added and mixed,
2N ammonium hydroxide was added to the resulting mixture to adjust its pH to 8.2.

Next, the mixture thus obtained was aged at 60 ° C. for 3 hours to gelate the silica sol contained in the mixture to obtain a gel in which silica gel was adhered and bound to the surfaces of zirconium hydroxide particles. The gel was separated from the liquid, washed with water, and filtered. The gel thus obtained was used as an additive component. SiO in this gel
_{The 2} / ZrO ₂ weight ratio was 0.11, and its SiO ₂ content was 10 wt%. In addition, the gel is 120 ℃
A part of the dried particles dried in (4) was calcined at 500 ° C. for 3 hours. The calcined product had a surface area of 127 m ² / g and a pore volume of 0.28 cc / g.

Example 3 (Preparation of Additive IIA) An aqueous solution of water glass having a SiO ₂ content of 8.5 wt% (p
2N sulfuric acid was added to 1200 g of H: 12) and the pH was adjusted to 3 to obtain a silica sol. Then, to 1450 g of this silica sol solution, 102 g of kaolin and 306 g of SiO ₂ —ZrO ₂ gel obtained in Reference Example 2 in dry weight conversion were added and uniformly dispersed, and then spray dried to obtain an average particle size of 60.
μm of additive IIA was obtained. The composition of this additive IIA is as follows: silica-zirconia 60 wt%, kaolin 20
It was wt% and silica 20 wt%. The total silicon content was 36 wt% in terms of SiO ₂ .

Comparative Example 1 (Preparation of Additives IIB and IIC) Kaolin and silica dispersed in a silica sol solution using silica-zirconia prepared in the same manner as in Reference Example 2 but having different silica contents. -Additives IIB, II were added in the same manner except that the amount of zirconia was variously changed.
I made C. The composition is shown in Table 3 together with the composition of the additive IIA obtained in Example 3.

Comparative Example 2 (Preparation of Additive IID) Additive IID was prepared in the same manner as in Example 3 except that alumina was used instead of silica-zirconia. The composition is shown in Table 3 together with the additives IIA, IIB and IIC obtained in Example 3 and Comparative Example 1.

The method of preparing the used alumina is as follows. While stirring, 1500 g of an aqueous solution of sodium aluminate (pH 14) having an Al ₂ O ₃ concentration of 10 wt% was added to Al ₂ O ₃
Aluminum sulfate aqueous solution having a concentration of 4.6 wt% (pH 3.
0) 1500 g was added to obtain a mixed water slurry having a pH of 9.5. The mixture thus obtained was aged at 60 ° C. for 3 hours, then the gel was separated from the liquid, washed with water, and filtered. This gel was dried at 120 ° C. to obtain 50 dry particles.
It was calcined at 0 ° C. for 3 hours. This fired product has a surface area of 300 m
² / g, and the pore volume was 0.35 cc / g.

Application Example 2 To perform a performance test of the additives obtained in Example 3 and Comparative Examples 1 and 2, after uniformly mixing the additives with the FCC catalyst,
This catalyst mixture was tested for microactivity test (MA
T) The apparatus was used to carry out fluid catalytic cracking reaction under the same feed oil and under the same conditions. The composition of the FCC catalyst is as shown in Table 3, and the amount of the additive added to the FCC catalyst is F
The amount was 10 parts by weight based on 100 parts by weight of the CC catalyst. As a comparative reference, it was carried out also when the additive was not added. Desulfurized VGO was used as the raw material heavy oil.
Prior to the test, the catalyst mixture consisting of the FCC catalyst and the additive was calcined at 650 ° C for 1 hour and then at 760 ° C for 1 hour.
It was treated in a 100% steam atmosphere for 6 hours. Furthermore, in order to carry out a hydrothermal stability test of the additive, the reaction was carried out in the MAT apparatus under the same conditions as in the application example 1 with and without the additive before and after the steam treatment. The results are shown in Table 4.

[0028]

[Table 3]

[0029]

[Table 4] * A comparative example is shown. ** A reference example is shown.

Front page continuation (72) Inventor Tadashi Miura 1-3-1, Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Corporation Research Laboratory (56) Reference JP-A-4-305247 (JP, A) JP-A 4-200744 (JP, A) JP-A-4-226187 (JP, A) JP-A-56-91841 (JP, A) JP-A-52-53789 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C10G 11/04-11/18 B01J 21/12-21/16

Claims (2)

(57) [Claims] 1. A fluid catalytic cracking catalyst additive consists zeolite and a porous inorganic oxide, silica - consists particulate mixture of alumina and clay and silica, said silica
The silica content in the carbon alumina is 10 to 30% by weight.
Ri, said additive, wherein the amount of silicon contained in the mixture is 10 to 60% by weight in terms of SiO _2. 2. Comprised of zeolite and porous inorganic oxide
As a fluid catalytic cracking catalyst additive,
It consists of a particulate mixture of luconia, clay and silica.
Silica content in rica-zirconia is 10 to 30% by weight
And the content of silicon contained in the mixture is SiO
Before being characterized by being 10 to 60% by weight in terms of ₂
Serial additives.