JP3467608B2 - Additive for fluid catalytic cracking catalyst of heavy oil - Google Patents

Description

BACKGROUND OF THE INVENTION [0001] Field of the Invention The present invention relates to additives to catalyst fluidized catalytic cracking of heavy oil (FCC).
It should be noted that the heavy oil referred to in this specification means a boiling point of 650 ° F. (3
43 ° C.) or higher. Examples of such heavy oils include various crude oils, residual distillation oils of these crude oils at normal pressure, reduced pressure distillation residues, solvent de-oiled oil, solvent de-oiled asphalt, shale oil, tar sand oil, and coal liquefied oil. In addition to the non-distilled oil, distillates such as HGO (normal pressure heavy gas oil) and VGO (vacuum gas oil), and mixtures of these distillates and the above-mentioned non-distillates are mentioned. [0002] Various methods are known for decomposing heavy oil to obtain light oil. As a typical method, fluid catalytic cracking (FCC) is known. I have. In such catalytic cracking of heavy oil, how to obtain light oil with high yield is one of the important issues, and many studies have been made to solve the problem. As one method for improving the light oil yield, it is known to mix an additive having an action of accelerating the decomposition of heavy components in heavy oil with a cracking catalyst. Heretofore, as such additives, those comprising alumina, clay and silica have been known. However, such a method has a problem that decomposition of heavy oil is not promoted or coke precipitation increases because the specific surface area is high and the acid amount and the acid strength distribution are not controlled. DISCLOSURE OF THE INVENTION The present invention is directed to fluid catalytic cracking of heavy oil which has a high cracking activity for heavy components in heavy oil and is also excellent in hydrothermal stability. Provides catalytic additives and fluid contact of heavy oil with less coke deposition
An object of the present invention is to provide an additive for a catalytic cracking catalyst . [0004] The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, zeolite and porous
Additive for fluid catalytic cracking catalyst composed of inorganic oxide
There, the silica - consists of alumina and clay and silica, all
10 to 60 wt% der in the content of silicon in terms of SiO ²
That consists particles, which has a total pore volume of the specific surface area and 0.14~0.45ml / g of 30~80m ² / g, volume of pores pore radius 60Å is 0.05 ml /
g or less, and the total acid content is 0.02 to 0.065.
The additive is provided, characterized in that the range of mmol / g. [0005] Silica-Al contained in the additive for catalytic cracking of heavy oil of the present invention (hereinafter also simply referred to as additive)
Mina having a silica content of 10 to 30% by weight, preferably 10 to 20% by weight is preferably used.
If the silica content is above this range, the hydrothermal stability of the additive will be poor, while if it is below this range,
The decomposition activity of heavy components is reduced. The silica-alumina used in the present invention is represented by physical properties of the calcined product, and its surface area is usually 150 to 450 m ² / g, preferably ^{2 to} 450 m ² / g.
00 to 350 m ² / g, and its pore volume is usually
0.2-1.5 cc / g, preferably 0.5-1.2 c
c / g. Further, the silica - as alumina, alumina as the core, the use of a structure in which silica is bonded in layers is not preferable on the surface. As clay, kaolin, bentonite,
Although there are Kibushi clay and the like, kaolin is preferably used. Generally, one containing one or more clay minerals such as kaolinite, dickite, nacrite, halloysite, and hydrohaloysite as a main component is used. In order to preferably produce the additive of the present invention,
Clay and silica-alumina gel are added to the silica sol solution, and the mixture is stirred uniformly to form a dispersion. In this case, the average particle size of the clay is 0.5 to 5 μm, preferably 2 to 3 μm. The average particle size of silica-alumina is 0.5 to 10 μm.
m, preferably 3 to 7 μm. The total solid content in the dispersion is 10 to 50% by weight, preferably 20 to 3% by weight.
0% by weight. Next, the dispersion thus obtained is spray-dried. The drying temperature in this case is 180 to 30
0 ° C, preferably 200-270 ° C. By this spray drying, the additive of the present invention is obtained in a powder form. The average particle size of the powder is 50 to 80 μm, preferably 55 to 7 μm.
0 μm. In addition, the dried product obtained in this manner is, if necessary, 300 to 700 ° C., preferably 400 ° C.
It is as possible de used in baking to 600 ° C.. In the additive of the present invention, the silica-a
Lumina content is 5 to 70% by weight, preferably 10 to 70% by weight.
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.
It is. Further, in the additive of the present invention, the total silicon content is preferably in the range of 10 to 60% by weight, preferably 20 to 50% by weight in terms of SiO ₂ .
If the total silicon content exceeds the above range, the hydrothermal stability of the additive will deteriorate, while if it is less than the above range, the decomposition activity for heavy components will decrease. In the additive of the present invention, its specific surface area is 30 to 80 m ² / g, preferably 40 to 60 m ² / g, and its total pore volume is 0.14 to 0.45 ml / g, preferably It is 0.20 to 0.40 ml / g. The pore volume (micropore volume) having a pore radius of 60 ° or less is 0.05 ml / g or less, and preferably 0.04 ml / g or less. Furthermore, the total acid content is 0.02-0.065 mm
ol / g, preferably 0.025 to 0.060 mmol
/ G. The additive of the present invention tends to increase the total acid content as its specific surface area increases.
When the specific surface area and the total acid amount exceed the above ranges, the effect of adding the heavy oil to the fluid catalytic cracking catalyst cannot be obtained, and the heavy oil catalytic cracking catalyst is not used alone. Conversion, naphtha yield and LCO
(Light cycle oil) No substantial improvement in yield. Moreover, the additive of this invention is 0.14-0.45 ml.
/ G of total pore volume, but the micropore volume with a pore radius of 60 ° or less is kept at 0.05 ml / g or less. If the micropore volume exceeds the above range, the effect of preventing coke formation will be insufficient. (Specific Surface Area) After holding 0.2 g of a sample under the conditions of 200 ° C. and 1 × 10 ⁻³ Torr for 1 hour, nitrogen gas is adsorbed at a liquid nitrogen temperature (77 K), and the adsorbed amount is measured. To determine the specific surface area. The BET method was used for the calculation. (Total pore volume) Following the above specific surface area measurement, at a liquid nitrogen temperature (77 K), after adsorbing nitrogen gas to a relative pressure of 1.0, desorption of nitrogen gas was performed to a relative pressure of 0.14. The pore volume was calculated from the amount of desorption. (Amount of total acid) After holding 0.5 g of the sample under the condition of 400 ° C. and 1 × 10 ⁻⁴ Torr for 4 hours, ammonia gas was adsorbed, and the heat of adsorption generated at that time was measured. 70KJ /
The amount of adsorbed ammonia of at least mol was defined as the total acid amount. In addition,
This measurement was performed using "adsorption heat measuring device" manufactured by Tokyo Riko Co., Ltd. The physical properties of the additive of the present invention can be adjusted by the production conditions. For example, the specific surface area and the total pore volume can be adjusted by adjusting the specific surface area of the silica-alumina to be added or by adjusting the particle size to adjust the reactivity with the silica sol. It can be adjusted by its specific surface area. The micropore volume can be adjusted by adjusting the reactivity of the silica sol with silica-alumina . [0013] Additives of the present invention is preferably used by mixing the FCC catalyst flour powder form. The FCC catalyst is composed of a porous inorganic oxide and zeolite. As the porous inorganic oxide, silica-alumina, silica-zirconia, silica-magnesia and the like are used. The additive of the present invention is particularly preferably applied to an FCC catalyst composed of zeolite, silica, alumina, and kaolin. The amount of the additive of the present invention added to the FCC catalyst is 2 to 30 parts by weight based on 100 parts by weight of the FCC catalyst.
Parts by weight, preferably 4 to 20 parts by weight. The additive of the present invention has a high decomposition activity for heavy components in heavy oil, especially for heavy components having a boiling point of 650 ° F. or more, and has a boiling point of 650 ° F. or less. Of light oils (naphtha and LCO) in high yield. 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 ) A 2N aqueous ammonium hydroxide solution was added to 7000 g of an aluminum sulfate aqueous solution (pH 3) having an Al ₂ O ₃ concentration of 1.3 wt%, and water having a pH of 8.2 was added. A water slurry containing aluminum oxide was obtained. On the other hand, when the SiO ₂ content is 5.8 w
2N sulfuric acid was added to 170 g of a t% aqueous water glass solution (pH 12) to adjust the pH to 3.0 to obtain a silica sol solution. Next, to this silica sol solution, the aqueous slurry of aluminum hydroxide obtained above was added and mixed under stirring, and 2N ammonium hydroxide was added to the obtained mixture,
The pH was adjusted to 8.2. Next, the mixture thus obtained was aged at 25 ° C. for 3 hours to gel the silica sol contained in the mixture, thereby obtaining a gel having silica gel adhered and bonded to the surface of the aluminum hydroxide particles. This 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 heated to 120 ° C.
Of the dried particles dried at 500 ° C. for 3 hours. This fired 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) An aqueous solution of water glass having a SiO ₂ content of 15.2 wt% (p
H: 12) 2N sulfuric acid was added to 660 g, and the p
H was adjusted to 3 to obtain a silica sol. Next, 100 g of kaolin and 300 g of the SiO ₂ —Al ₂ O ₃ gel obtained in Reference Example 1 in terms of dry weight were added to 1180 g of the silica sol solution, uniformly dispersed, and then spray-dried.
μm of additive A was obtained. The composition of the additive A is as follows: silica-alumina 60 wt%, kaolin 20 wt%
% And 20 wt% of silica. The total silicon content was 26 wt% in terms of SiO ₂ . Example 2 (Preparation of Additives BF) In Example 1, S was prepared in the same manner as in Reference Example 1.
with the use of different silica-alumina of iO ₂ content, silica sol, kaolin, silica - except that the amount of alumina was varied in the same manner to make a additive B to F. 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 conduct a performance test of the additives obtained in Examples 1 and 2, after uniformly mixing the additives with the FCC catalyst, the catalyst mixture was subjected to a micro-activity test (MAT) apparatus. The fluid catalytic cracking reaction was carried out under the same feedstock and under the same conditions. The composition of the FCC catalyst is as shown in Table 1,
The amount of the additive to the FCC catalyst was 10 parts by weight based on 100 parts by weight of the FCC catalyst. For comparison, a case where no additive was added was also performed.
Desulfurized VGO was used as the raw material heavy oil. Also,
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 treated at 760 ° C. for 16 hours in a 100% steam atmosphere. Further, in order to conduct a hydrothermal stability test of the additives, the additives before and after the steam treatment were reacted with the MAT apparatus using only the additives. Table 2 shows the results. 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 indicated conversion, naphtha yield,
The LCO yield and coke yield are defined by the following equations. (1) Conversion (wt%) = (AB) / A × 100 A: Weight of feedstock B: Weight of fraction of boiling point 221 ° C. or higher in product oil (2) Naphtha yield (wt%) = C / A × 100 C: Weight of naphtha (boiling range: C _{5 to} 221 ° C.) in product oil (3) LCO yield (wt%) = D / A × 100 D: LCO in product oil (boiling point (Range: 221 to 343 ° C)
Weight of coke (4) Coke yield (wt%) = E / A × 100 E: Weight of coke deposited on catalyst mixture [Table 2]

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Tadashi Miura 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. Research Institute (56) References JP-A-56-91841 (JP, A) JP-A-52-53789 (JP, A) JP-A-61-238345 (JP, A) JP-A-8-5044397 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C10G 11/02-11/08 C10G 11/18 B01J 21/12-21/16 B01J 32/00

Claims (1)

(57) [Claims] [Claim 1] Consisting of zeolite and porous inorganic oxide
A fluid catalytic cracking catalyst additive,
Lumin , clay and silica, total silicon content is S
3 to 10% by weight in terms of iO ₂
0-80 m ² / g specific surface area and 0.14-0.45 m
1 / g total pore volume and a pore radius of 60 °
The above-mentioned additive, wherein the following pore volume is 0.05 ml / g or less, and the total acid content is in a range of 0.02 to 0.065 mmol / g.